WO2016072780A1 - Organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

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

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WO2016072780A1
WO2016072780A1 PCT/KR2015/011888 KR2015011888W WO2016072780A1 WO 2016072780 A1 WO2016072780 A1 WO 2016072780A1 KR 2015011888 W KR2015011888 W KR 2015011888W WO 2016072780 A1 WO2016072780 A1 WO 2016072780A1
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substituted
compound
unsubstituted
organic electroluminescent
mixture
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French (fr)
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Hyun Kim
So-Young Jung
Sung-Woo Jang
Ga-Won Lee
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority claimed from KR1020150111327A external-priority patent/KR101636310B1/en
Application filed by Rohm and Haas Electronic Materials Korea Ltd filed Critical Rohm and Haas Electronic Materials Korea Ltd
Priority to CN201580056636.0A priority Critical patent/CN107075362B/en
Priority to US15/521,904 priority patent/US10033001B2/en
Publication of WO2016072780A1 publication Critical patent/WO2016072780A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • 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
    • 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
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present disclosure relates to an organic electroluminescent compound and an 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 organic EL device has a structure comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode.
  • the organic layer of the organic EL device comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc.
  • the energy of excitons puts the light-emitting organic compound in an excited state, and the decay of the excited state results in a relaxation of the energy level into a ground state, accompanied by light-emission. Therefore, the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • the light-emitting materials can be classified as a host material and a dopant material.
  • devices showing good electroluminescent characteristics comprise a light-emitting layer in which a dopant is doped into a host.
  • the dopant/host system is provided to enhance luminous efficiency through energy transfer from a host to a dopant.
  • the dopant and host materials highly affect efficiencies and lifespan of the device.
  • 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)picolinate iridium (Firpic) as red-, green-, and blue-emitting materials, respectively.
  • Iridium(III) complex-based dopant compounds showing better characteristics, i.e., long lifespan, high efficiency, and high color purity must be urgently developed.
  • pixels which show particular colors called as a “saturated” color are required, and especially, saturated red, green, and blue pixels are required, which can be measured by a CIE coordinate known in this field.
  • CIE coordinate known in this field.
  • each of red, green, and blue should have high color purity. In the case of red, color purity becomes higher, as it approaches a deep-red coordinate around 0.680 of x-axis of CIE. A dopant compound which meets such requirements is desired.
  • Korean Patent No. 0662381, Korean Patent Application Laying-Open No. 2011-0086021, WO 2008/109824, and WO 2010/033550 disclose iridium complexes having 2-phenylquinoline-based ligand, as a dopant compound of an organic electroluminescent device.
  • said prior arts fail to specifically disclose an iridium complex having a ligand in which quinoline of 2-phenylquinoline is substituted with alkyl at 4-position and is substituted with phenyl at 6-position.
  • the object of the present disclosure is to provide a compound which can be used to prepare an organic electroluminescent device showing good color purity and long lifespan, and to provide an organic electroluminescent device comprising the compound.
  • R 1 and R 2 each independently, represent a (C1-C5)alkyl
  • R 3 represents a (C3-C5)alkyl unsubstituted or substituted with deuterium
  • R 4 represents phenyl unsubstituted or substituted with a (C1-C5)alkyl unsubstituted or substituted with deuterium
  • R 5 and R 6 each independently, represent methyl unsubstituted or substituted with deuterium.
  • the compound of the present disclosure can provide an organic electroluminescent device showing remarkably improved color purity and lifespan.
  • Phenyl is generally an electron-donating group, but in the present disclosure, is used as an electron-withdrawing group.
  • phenyl is introduced as an electron-withdrawing group at R 4 position of quinoline which affects LUMO energy level of the molecule, thereby reducing electron density and lowering LUMO energy level. Due to the lowered LUMO energy level, an energy gap between HOMO energy level and LUMO energy level becomes smaller. As a result, color purity of a red-emitting organic electroluminescent device is improved.
  • the present disclosure provides the compound of formula 1 above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the compound.
  • a "(C1-C5)alkyl” indicates a linear or branched alkyl having 1 to 5 carbon atoms.
  • a (C1-C5)alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
  • R 1 and R 2 each independently, represent a (C1-C5)alkyl.
  • R 1 and R 2 each independently, may be selected from methyl, ethyl, and a branched (C3-C5)alkyl.
  • R 1 and R 2 may be the same.
  • R 3 represents a (C3-C5)alkyl unsubstituted or substituted with deuterium. Specifically, R 3 may be selected from isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
  • R 3 may be selected from isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
  • R 4 represents phenyl unsubstituted or substituted with a (C1-C5)alkyl unsubstituted or substituted with deuterium.
  • R 4 may be phenyl unsubstituted or substituted with a (C1-C3)alkyl. More specifically, R 4 may be selected from phenyl, phenyl substituted with methyl, phenyl substituted with deuterium-substituted methyl, phenyl substituted with isopropyl, phenyl substituted with isobutyl, phenyl substituted with tert-butyl, and phenyl substituted with 2,2-dimethylpropyl.
  • R 4 may be phenyl unsubstituted or substituted with a (C1-C4)alkyl.
  • R 3 may be selected from a branched (C3-C5)alkyl unsubstituted or substituted with deuterium, and R 4 may be phenyl unsubstituted or substituted with methyl unsubstituted or substituted with deuterium.
  • the compound of formula 1 includes the following, but is not limited thereto.
  • the compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
  • R 1 to R 6 are as defined in formula 1.
  • the present disclosure provides an organic electroluminescent material comprising the compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material.
  • 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 blocking layer, and an electron buffer layer.
  • the compound of formula 1 of the present disclosure may be comprised as a dopant material in the light-emitting layer.
  • the light-emitting layer may further comprise at least one host material.
  • a host material which may be used to be comprised with the compound of the present disclosure includes the compound of formula 2:
  • Ma represents a substituted or unsubstituted nitrogen-containing 5- to 11-membered heteroaryl
  • La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene
  • Xa to Xh each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or un
  • La may be a single bond, or a substituted or unsubstituted (C6-C12)arylene. More preferably, La may be a single bond, or a (C6-C12)arylene unsubstituted or substituted with a tri(C6-C10)arylsilyl. Specifically, La may be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
  • Ma may be a substituted or unsubstituted nitrogen-containing 5- to 11-membered heteroaryl. More preferably, Ma may be a nitrogen-containing 6- to 11-membered heteroaryl unsubstituted or substituted with a cyano, a (C1-C6)alkyl, a tri(C6-C12)arylsilyl, a (C6-C18)aryl, or a 5- to 15-membered heteroaryl.
  • Ma may be a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted tetrazinyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted tetrazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridazinyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted isoindolyl, a substituted or unsubstituted indolyl,
  • Ma may be a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthylidinyl, or a substituted or unsubstituted quinoxalinyl.
  • Xa to Xh each independently, may be hydrogen, a cyano, a substituted or unsubstituted (C6-C15)aryl, a substituted or unsubstituted 6- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C15)arylsilyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstitued 6- to 20-membered, mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  • Xa to Xh may be hydrogen; a cyano; a (C6-C15)aryl unsubstitued or substituted with a tri(C6-C10)arylsilyl; or a 10- to 20-musined heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
  • At least one of Xa to Xh may be a substituted or unsubstituted dibenzothiophene; a substituted or unsubstituted dibenzofuran; a substituted or unsubstituted carbazole; a substituted or unsubstituted benzocarbazole; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
  • the compound of formula 2 includes the following, but is not limited thereto:
  • a combination of the compound of formula 1 and the compound of formula 2, and an organic electroluminescent device comprising the combination are provided.
  • a mixture or composition for preparing an organic electroluminescent device comprises the compound of formula 1.
  • the mixture or composition may be the one for preparing a light-emitting layer of an organic electroluminescent device.
  • the mixture or composition may further comprise the host compound of formula 2, in addition to a compound of the present disclosure.
  • the mixture or composition may comprise the compound of formula 1 to be combined with the host compound of formula 2.
  • the mixture or composition may further comprise a conventional material which has been used to prepare an organic electroluminescent device.
  • 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 a light-emitting layer 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 art, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow 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 organic electroluminescent device
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an OLED (Geomatec) was subjected to an ultrasonic washing with 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.
  • HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr.
  • HI-2 was then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • HT-1 was introduced into one cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • HT-2 was introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • compound H2-16 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and a dopant material shown in Table 1 below 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 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to produce OLED.
  • OLED was produced in the same manner as in Device Examples 1-1 to 1-5, except that a dopant shown in Table 1 below was used as a dopant for a light-emitting layer.
  • the data (voltage and color coordinates) of Device Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 shown in Table 1 were measured at a luminance of 1000 cd/m 2 , except lifespan. Said lifespan is the time taken to be 97% of the luminance when the early luminance at 5000 cd/m 2 and a constant current is taken as 100% of the luminance.
  • the color gamut is calculated based on a color space which was made by US National Television System Committee (NTSC) in view of the color coordinate system defined by the CIE of the International Commission on Illumination.
  • An area (t 0 ) of triangle made by three points of red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08) defined by the NTSC was determined, and then, an area (t 1 ) of triangle made by blue and green points defined by the NTSC and a red point described in Table 1 above was determined.
  • color gamut (%) [ t 1 (the area of color coordinate made by the present disclosure) / t 0 (an area of color coordinate based on NTSC standards) ] * 100.
  • the numerical value of the color gamut is larger and larger, the device can display a larger and larger number of colors. Therefore, the color gamut is better when it has a larger numerical value.
  • organic electroluminescent compound of the present disclosure By using the organic electroluminescent compound of the present disclosure, an organic electroluminescent device showing better color purity and lifespan is provided, compared with conventional organic electroluminescent compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound of the present disclosure can provide an organic electroluminescent device showing excellence in color purity, solubility, heat stability, driving voltage, current efficiency, and power efficiency, as well as remarkably improved lifespan.

Description

ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to an organic electroluminescent compound and an 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].
Generally, the organic EL device has a structure comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer of the organic EL device comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. When a voltage is applied to the organic EL device, holes and electrons are injected from an anode and a cathode, respectively, to the light-emitting layer. Excitons having high energy are formed by recombinations between the holes and the electrons. The energy of excitons puts the light-emitting organic compound in an excited state, and the decay of the excited state results in a relaxation of the energy level into a ground state, accompanied by light-emission. Therefore, the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
Depending on its function, the light-emitting materials can be classified as a host material and a dopant material. Generally, devices showing good electroluminescent characteristics comprise a light-emitting layer in which a dopant is doped into a host. The dopant/host system is provided to enhance luminous efficiency through energy transfer from a host to a dopant. In the dopant/host material system, the dopant and host materials highly affect efficiencies and lifespan of the device.
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)picolinate iridium (Firpic) as red-, green-, and blue-emitting materials, respectively.
However, considering EL characteristic requirements for a middle or large-sized panel of OLED, Iridium(III) complex-based dopant compounds showing better characteristics, i.e., long lifespan, high efficiency, and high color purity must be urgently developed.
Particularly, for a full-color display, pixels which show particular colors called as a “saturated” color are required, and especially, saturated red, green, and blue pixels are required, which can be measured by a CIE coordinate known in this field. In order to display more various colors, each of red, green, and blue should have high color purity. In the case of red, color purity becomes higher, as it approaches a deep-red coordinate around 0.680 of x-axis of CIE. A dopant compound which meets such requirements is desired.
Korean Patent No. 0662381, Korean Patent Application Laying-Open No. 2011-0086021, WO 2008/109824, and WO 2010/033550 disclose iridium complexes having 2-phenylquinoline-based ligand, as a dopant compound of an organic electroluminescent device. However, said prior arts fail to specifically disclose an iridium complex having a ligand in which quinoline of 2-phenylquinoline is substituted with alkyl at 4-position and is substituted with phenyl at 6-position.
The object of the present disclosure is to provide a compound which can be used to prepare an organic electroluminescent device showing good color purity and long lifespan, and to provide an organic electroluminescent device comprising the compound.
The present inventors found that the above object can be achieved by a compound represented by the following formula 1.
Figure PCTKR2015011888-appb-I000001
wherein
R1 and R2, each independently, represent a (C1-C5)alkyl,
R3 represents a (C3-C5)alkyl unsubstituted or substituted with deuterium,
R4 represents phenyl unsubstituted or substituted with a (C1-C5)alkyl unsubstituted or substituted with deuterium, and
R5 and R6, each independently, represent methyl unsubstituted or substituted with deuterium.
The compound of the present disclosure can provide an organic electroluminescent device showing remarkably improved color purity and lifespan.
An electron-donating property and an electron-withdrawing property between two materials exchanging electrons are not absolutely determined, but relatively determined depending on relation between the materials. Phenyl is generally an electron-donating group, but in the present disclosure, is used as an electron-withdrawing group. In formula 1, phenyl is introduced as an electron-withdrawing group at R4 position of quinoline which affects LUMO energy level of the molecule, thereby reducing electron density and lowering LUMO energy level. Due to the lowered LUMO energy level, an energy gap between HOMO energy level and LUMO energy level becomes smaller. As a result, color purity of a red-emitting organic electroluminescent device is improved.
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 compound of formula 1 above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the compound.
The details of the compound of formula 1 are as follows.
Herein, a "(C1-C5)alkyl" indicates a linear or branched alkyl having 1 to 5 carbon atoms. Specifically, a (C1-C5)alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
In formula 1, R1 and R2, each independently, represent a (C1-C5)alkyl. Specifically, R1 and R2, each independently, may be selected from methyl, ethyl, and a branched (C3-C5)alkyl. Preferably, R1 and R2 may be the same.
In formula 1, R3 represents a (C3-C5)alkyl unsubstituted or substituted with deuterium. Specifically, R3 may be selected from isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl. More specifically, R3 may be selected from isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
In formula 1, R4 represents phenyl unsubstituted or substituted with a (C1-C5)alkyl unsubstituted or substituted with deuterium. Specifically, R4 may be phenyl unsubstituted or substituted with a (C1-C3)alkyl. More specifically, R4 may be selected from phenyl, phenyl substituted with methyl, phenyl substituted with deuterium-substituted methyl, phenyl substituted with isopropyl, phenyl substituted with isobutyl, phenyl substituted with tert-butyl, and phenyl substituted with 2,2-dimethylpropyl.
According to one embodiment of the present disclosure, in formula 1, R4 may be phenyl unsubstituted or substituted with a (C1-C4)alkyl.
According to another embodiment of the present disclosure, in formula 1, R3 may be selected from a branched (C3-C5)alkyl unsubstituted or substituted with deuterium, and R4 may be phenyl unsubstituted or substituted with methyl unsubstituted or substituted with deuterium.
More specifically, the compound of formula 1 includes the following, but is not limited thereto.
Figure PCTKR2015011888-appb-I000002
Figure PCTKR2015011888-appb-I000003
Figure PCTKR2015011888-appb-I000004
Figure PCTKR2015011888-appb-I000005
Figure PCTKR2015011888-appb-I000006
The compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
Figure PCTKR2015011888-appb-I000007
In reaction scheme 1, R1 to R6 are as defined in formula 1.
In addition, the present disclosure provides an organic electroluminescent material comprising the compound of formula 1, and an organic electroluminescent device comprising the material.
The material may consist of the compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material.
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 blocking layer, and an electron buffer layer.
The compound of formula 1 of the present disclosure may be comprised as a dopant material in the light-emitting layer. The light-emitting layer may further comprise at least one host material.
A host material which may be used to be comprised with the compound of the present disclosure includes the compound of formula 2:
Figure PCTKR2015011888-appb-I000008
wherein
Ma represents a substituted or unsubstituted nitrogen-containing 5- to 11-membered heteroaryl;
La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene;
Xa to Xh, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 (C1-C30)alkyl(C6-C30)arylamino, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), 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 the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si, and P.
In formula 2, the substituent for the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, the substituted aryl, the substituted heteroaryl, the substituted trialkylsilyl, the substituted triarylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted alkylarylamino, the substituted monoarylamino, the substituted diarylamino, or the substituted mono- or polycyclic, alicyclic or aromatic ring, each independently, may be at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxy; 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 tri(C6-C30)arylsilyl, a (C6-C30)aryl, a (C1-C30)alkyl(C6-C30)aryl, or a tri(C6-C30)arylsilyl(C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl, a halogen, a (C6-C30)aryl, or 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.
In formula 2, preferably, La may be a single bond, or a substituted or unsubstituted (C6-C12)arylene. More preferably, La may be a single bond, or a (C6-C12)arylene unsubstituted or substituted with a tri(C6-C10)arylsilyl. Specifically, La may be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
In formula 2, preferably, Ma may be a substituted or unsubstituted nitrogen-containing 5- to 11-membered heteroaryl. More preferably, Ma may be a nitrogen-containing 6- to 11-membered heteroaryl unsubstituted or substituted with a cyano, a (C1-C6)alkyl, a tri(C6-C12)arylsilyl, a (C6-C18)aryl, or a 5- to 15-membered heteroaryl.
Specifically, Ma may be a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted tetrazinyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted tetrazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridazinyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted isoindolyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted indazolyl, a substituted or unsubstituted benzothiadiazolyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted cinnolinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthylidinyl, or a substituted or unsubstituted quinoxalinyl. More specifically, Ma may be a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthylidinyl, or a substituted or unsubstituted quinoxalinyl.
In formula 2, preferably, Xa to Xh, each independently, may be hydrogen, a cyano, a substituted or unsubstituted (C6-C15)aryl, a substituted or unsubstituted 6- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C15)arylsilyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstitued 6- to 20-membered, mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur. More preferably, Xa to Xh, each independently, may be hydrogen; a cyano; a (C6-C15)aryl unsubstitued or substituted with a tri(C6-C10)arylsilyl; or a 10- to 20-membred heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene. Specifically, at least one of Xa to Xh, for example, Xb, Xc, Xf, or Xg, may be a substituted or unsubstituted dibenzothiophene; a substituted or unsubstituted dibenzofuran; a substituted or unsubstituted carbazole; a substituted or unsubstituted benzocarbazole; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
More specifically, the compound of formula 2 includes the following, but is not limited thereto:
Figure PCTKR2015011888-appb-I000009
Figure PCTKR2015011888-appb-I000010
Figure PCTKR2015011888-appb-I000011
Figure PCTKR2015011888-appb-I000012
Figure PCTKR2015011888-appb-I000013
Figure PCTKR2015011888-appb-I000014
Figure PCTKR2015011888-appb-I000015
Figure PCTKR2015011888-appb-I000016
Figure PCTKR2015011888-appb-I000017
Figure PCTKR2015011888-appb-I000018
Figure PCTKR2015011888-appb-I000019
Figure PCTKR2015011888-appb-I000020
Figure PCTKR2015011888-appb-I000021
Figure PCTKR2015011888-appb-I000022
Figure PCTKR2015011888-appb-I000023
Figure PCTKR2015011888-appb-I000024
Figure PCTKR2015011888-appb-I000025
Figure PCTKR2015011888-appb-I000026
Figure PCTKR2015011888-appb-I000027
Figure PCTKR2015011888-appb-I000028
Figure PCTKR2015011888-appb-I000029
Figure PCTKR2015011888-appb-I000030
Figure PCTKR2015011888-appb-I000031
Figure PCTKR2015011888-appb-I000032
Figure PCTKR2015011888-appb-I000033
Figure PCTKR2015011888-appb-I000034
Figure PCTKR2015011888-appb-I000035
Figure PCTKR2015011888-appb-I000036
Figure PCTKR2015011888-appb-I000037
Figure PCTKR2015011888-appb-I000038
Figure PCTKR2015011888-appb-I000039
Figure PCTKR2015011888-appb-I000040
Figure PCTKR2015011888-appb-I000041
Figure PCTKR2015011888-appb-I000042
Figure PCTKR2015011888-appb-I000043
Figure PCTKR2015011888-appb-I000044
Figure PCTKR2015011888-appb-I000045
Figure PCTKR2015011888-appb-I000046
Figure PCTKR2015011888-appb-I000047
Figure PCTKR2015011888-appb-I000048
Figure PCTKR2015011888-appb-I000049
Figure PCTKR2015011888-appb-I000050
Figure PCTKR2015011888-appb-I000051
Figure PCTKR2015011888-appb-I000052
Figure PCTKR2015011888-appb-I000053
Figure PCTKR2015011888-appb-I000054
Figure PCTKR2015011888-appb-I000055
Figure PCTKR2015011888-appb-I000056
Figure PCTKR2015011888-appb-I000057
Figure PCTKR2015011888-appb-I000058
Figure PCTKR2015011888-appb-I000059
Figure PCTKR2015011888-appb-I000060
Figure PCTKR2015011888-appb-I000061
Figure PCTKR2015011888-appb-I000062
Figure PCTKR2015011888-appb-I000063
Figure PCTKR2015011888-appb-I000064
Figure PCTKR2015011888-appb-I000065
Figure PCTKR2015011888-appb-I000066
Figure PCTKR2015011888-appb-I000067
Figure PCTKR2015011888-appb-I000068
Figure PCTKR2015011888-appb-I000069
Figure PCTKR2015011888-appb-I000070
According to an additional aspect of the present disclosure, a combination of the compound of formula 1 and the compound of formula 2, and an organic electroluminescent device comprising the combination are provided.
According to an additional aspect of the present disclosure, a mixture or composition for preparing an organic electroluminescent device is provided. The mixture or composition comprises the compound of formula 1. The mixture or composition may be the one for preparing a light-emitting layer of an organic electroluminescent device. The mixture or composition may further comprise the host compound of formula 2, in addition to a compound of the present disclosure. The mixture or composition may comprise the compound of formula 1 to be combined with the host compound of formula 2. The mixture or composition may further comprise a conventional material which has been used to prepare an organic electroluminescent device.
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 a light-emitting layer 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 art, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow 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 D-1
Figure PCTKR2015011888-appb-I000071
Figure PCTKR2015011888-appb-I000072
Figure PCTKR2015011888-appb-I000073
Preparation of compound 1-1
After introducing malonic acid (23g, 222mmol) and POCl3 (161mL, 1729mmol) into a reaction vessel, the mixture was stirred at room temperature for 10 minutes. [1,1'-biphenyl]-4-amine (25g, 148mmol) was slowly added dropwise to the mixture. Afterward, the mixture was stirred at 150℃. After slowly adding H2O dropwise to the mixture, the mixture was extracted with methylene chloride (MC), and a solvent was removed therefrom. The obtained substance was subjected to column chromatography to obtain compound 1-1 (20g, 50%).
Preparation of compound 1-2
After introducing compound 1-1 (19.5g, 92mmol), (3,5-dimethylphenyl)boronic acid (13.8g, 92mmol), Pd(PPh3)4 (3.2g, 3mmol), K2CO3 (38g, 276mmol), toluene (383mL), and H2O (128mL) into a reaction vessel, the mixture was under reflux at 120℃, cooled to room temperature, and then extracted with ethyl acetate and H2O. The extracted organic layer was subjected to column chromatography to obtain compound 1-2 (15g, 47%).
Preparation of compound 1-3
After introducing compound 1-2 (14.5g, 42mmol), isobutyl boronic acid (8.6g, 84mmol), S-Phos (1.38g, 3.37mmol), K3PO4 (43.86g, 207mmol), Pd2(dba)3 (1.55g, 1.7mmol), and toluene (280mL), the mixture was stirred for 12 hous. The mixture was cooled to room temperature, and extracted with ethyl acetate and H2O. The extracted organic layer was subjected to column chromatography to obtain compound 1-3 (6.5g, 42%).
Preparation of compound 1-4
After introducing compound 1-3 (6.5g, 18mmol), IrCl3˙xH2O (2.4g, 8mmol), 2-ethoxyethanol (136mL), and H2O (68mL) into a reaction vessel, the mixture was under reflux at 130℃ for 24hours. The mixture was cooled to room temperature, and H2O was added thereto. The mixture was stirred for 30 minutes, and filtered to obtain a solid, compound 1-4 (4.8g, 63%).
Preparation of compound D-1
After introducing compound 1-4 (4.8g, 2.5mmol), pentan-2,4-dione (2.6mL, 25mmol), Na2CO3 (0.83g, 7.8mmol), and 2-ethoxyethanol (10mL) into a reaction vessel, the mixture was reacted at room temperature overnight. The mixture was filtered, and the obtained solid was subjected to column chromatography to obtain compound D-1 (2g, 39%).
Figure PCTKR2015011888-appb-I000074
Example 2: Preparation of compound D-2
Figure PCTKR2015011888-appb-I000075
After introducing compound 1-4 (8.0g, 4.2mmol), compound 8 (7.9mL, 41.8mmol), K2CO3 (5.78g, 41.8mmol), and 2-ethoxyethanol (50mL) into a reaction vessel, the mixture was reacted at room temperature for 24 hours. The mixture was filtered, and the obtained solid was subjected to column chromatography to obtain compound D-2 (1.6g, 35%).
Figure PCTKR2015011888-appb-I000076
Example 3: Preparation of compound D-7
Figure PCTKR2015011888-appb-I000077
Figure PCTKR2015011888-appb-I000078
Preparation of compound 7-3
After introducing compound 7-2 (34g, 327mmol) and POCl3 (218mL, 2342mmol) into a reaction vessel, the mixture was stirred at room temperature for 10 minutes. After slowly adding compound 7-1 (40g, 218mmol) dropwise to the mixture, the mixture was stirred at 150℃. After slowly adding H2O dropwise, the mixture was extracted with MC, and the solvent was removed therefrom. The remaining substance was subjected to column chromatography to obtain compound 7-3 (34g, 44%).
Preparation of compound 7-5
After introducing compound 7-3 (33g, 116mmol), compound 7-4 (21g, 139mmol), Pd(PPh3)4 (4.01g, 3.47mmol), K2CO3 (48g, 347mmol), toluene (500mL), and H2O (173mL) into a reaction vessel, the mixture was stirred under reflux at 120℃. The mixture was cooled to room temperature, extracted with ethyl acetate and H2O, and subjected to column chromatography to obtain compound 7-5 (28g, 68%).
Preparation of compound 7-6
After introducing compound 7-5 (27g, 75.4 mmol), isobutyl boronic acid (15.4g, 150.9mmol), S-Phos (2.5g, 6mmol), K3PO4 (78.4g, 369mmol), Pd2(dba)3 (2.76g, 3mmol), and toluene (300mL) into a reaction vessel, the mixture was stirred for 5 hours. The mixture was cooled to room temperature, extracted with ethyl acetate and H2O, and subjected to column chromatography to obtain compound 7-6 (20g, 69%).
Preparation of compound 7-7
After introducing compound 7-6(20g, 52.7mmol), IrCl3 ㆍxH2O (7.2g, 23.9mmol), 2-ethoxyethanol (210mL), and H2O (70mL) into a reaction vessel, the mixture was stirred under reflux at 130℃ for 24 hours. The mixture was cooled to room temperature, and H2O was added thereto. The mixture was stirred for 30 minutes, and fitered to obtain a solid, compound 7-7 (12g, 51%).
Preparation of compound D-7
After introducing compound 7-7 (6g, 3mmol), compound 7-8 (3.1mL, 30mmol), K2CO3 (4.1g, 30mmol), and 2-ethoxyethanol (50mL) into a reaction vessel, the mixture was reacted at room temperature for 24 hours. The mixture was filted, and the obtained solid was subjected to column chromatography to obtain compound D-7 (1.5g, 23.8%).
Figure PCTKR2015011888-appb-I000079
Example 4: Preparation of compound D-10
Figure PCTKR2015011888-appb-I000080
After introducing compound 7-7 (6g, 3mmol), compound 10-8 (4mL, 17.3mmol), K2CO3(4.8g, 30mmol), and 2-ethoxyethanol (60mL) into a reaction vessel, the mixture was reacted at room temperature for 24 hours. The mixture was filtered and subjected to column chromatography to obtain compound D-10 (1.8g, 23%).
Figure PCTKR2015011888-appb-I000081
Example 5: Preparation of compound D-13
Figure PCTKR2015011888-appb-I000082
After introducing compound 7-7 (9g, 4.6mmol), compound 20-8 (8.4g, 46mmol), Na2CO3 (4.9g, 46mmol), and 2-ethoxyethanol (57mL) into a reaction vessel, the mixture was reacted at room temperature overnight. The mixture was filtered, and the obtained solid was subjected to column chromatography to obtain compound D-13 (1g, 10%).
Figure PCTKR2015011888-appb-I000083
Example 6: Preparation of compound D-20
Figure PCTKR2015011888-appb-I000084
Figure PCTKR2015011888-appb-I000085
Preparation of compound 20-3
After introducing compound 20-2 (23g, 222mmol) and POCl3 (161mL, 1729mmol) into a reaction vessel, the mixture was stirred at room temperature for 10 minutes. After slowly adding compound 20-1 (25g, 148mmol) dropwise, the mixture was stirred at 150℃. After slowly adding H2O dropwise, the mixture was extracted with MC, and the solvent was removed thereform. The remaining substance was subjected to column chromatography to obtain compound 20-3 (20g, 50%).
Preparation of compound 20-5
After introducing compound 20-3 (19.5g, 92mmol), compound 20-4 (13.8g, 92mmol), Pd(PPh3)4 (3.2g, 3mmol), K2CO3 (38g, 276mmol), toluene (383mL), and H2O (128mL) into a reaction vessel, the mixture was under reflux at 120℃. The mixture was cooled to room temperature, extracted with ethyl acetate and H2O, and subjected to column chromatography to obtain compound 20-5 (15g, 47%).
Preparation of compound 20-6
After introducing compound 20-5 (15g, 43mmol), isobutylboronic acid (8.9g, 87mmol), S-Phos (1.4g, 3.49mmol), K3PO4 (45g, 213mmol), Pd2(dba)3 (1.6g, 1.7mmol), and toluene (290mL) into a reaction vessel, the mixture was stirred for 12 hours. The mixture was cooled to room temperature, extracted with ethyl acetate and H2O, and subjected to column chromatography to obtain compound 20-6 (12.2g, 77%).
Preparation of compound 20-7
After introducing compound 20-6 (12g, 33mmol), IrCl3 ㆍxH2O (4.5g, 15mmol), 2-ethoxyethanol (115mL), and H2O (55mL) into a reaction vessel, the mixture was under reflux at 130℃ for 24 hours. The mixture was cooled to room temperature, and H2O was added thereto. The mixture was stirred for 30 minutes, and filtered to obtain a solid, compound 20-7 (8g, 57%).
Preparation of compound D-20
After introducing compound 20-7 (8g, 4.2mmol), compound 20-8 (7.7g, 42mmol), Na2CO3 (4.4g, 42mmol), and 2-ethoxyethanol (50mL) into a reaction vessel, the mixture was reacted at room temperature overnight. The mixture was filtered, and the obtained solid was subjected to column chromatography to obtain compound D-20 (2.2g, 24%).
Figure PCTKR2015011888-appb-I000086
[Device Examples 1-1 to 1-5] OLED comprising the dopant of the present disclosure
An organic electroluminescent device (OLED) was produced using the light-emitting compound of the present disclosure as follows. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an OLED (Geomatec) was subjected to an ultrasonic washing with 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. HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. HI-2 was then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. HT-1 was introduced into one cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. HT-2 was introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. Thereafter, compound H2-16 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and a dopant material shown in Table 1 below 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 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing EI-1 as an electron injection layer having a thickness of 2 nm, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to produce OLED.
Figure PCTKR2015011888-appb-I000087
[Comparative Examples 1-1 to 1-4] OLED using a conventional organic
electroluminescent compound
OLED was produced in the same manner as in Device Examples 1-1 to 1-5, except that a dopant shown in Table 1 below was used as a dopant for a light-emitting layer.
Figure PCTKR2015011888-appb-I000088
Organic electroluminescent devices produced in Device Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 were characterized as shown in Table 1 below.
Figure PCTKR2015011888-appb-I000089
The data (voltage and color coordinates) of Device Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 shown in Table 1 were measured at a luminance of 1000 cd/m2, except lifespan. Said lifespan is the time taken to be 97% of the luminance when the early luminance at 5000 cd/m2 and a constant current is taken as 100% of the luminance.
The color gamut is calculated based on a color space which was made by US National Television System Committee (NTSC) in view of the color coordinate system defined by the CIE of the International Commission on Illumination. An area (t0) of triangle made by three points of red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08) defined by the NTSC was determined, and then, an area (t1) of triangle made by blue and green points defined by the NTSC and a red point described in Table 1 above was determined. Thereafter, color gamut (%) was calculated as follows: Color gamut (%) = [ t1 (the area of color coordinate made by the present disclosure) / t0 (an area of color coordinate based on NTSC standards) ] * 100. Where the numerical value of the color gamut is larger and larger, the device can display a larger and larger number of colors. Therefore, the color gamut is better when it has a larger numerical value.
By using the organic electroluminescent compound of the present disclosure, an organic electroluminescent device showing better color purity and lifespan is provided, compared with conventional organic electroluminescent compound.

Claims (6)

  1. A compound represented by the following formula 1:
    Figure PCTKR2015011888-appb-I000090
    wherein
    R1 and R2, each independently, represent a (C1-C5)alkyl,
    R3 represents a (C3-C5)alkyl unsubstituted or substituted with deuterium,
    R4 represents phenyl unsubstituted or substituted with a (C1-C5)alkyl unsubstituted or substituted with deuterium, and
    R5 and R6, each independently, represent methyl unsubstituted or substituted with deuterium.
  2. The compound according to claim 1, wherein R4 is phenyl unsubstituted or substituted with a (C1-C4)alkyl.
  3. The compound according to claim 1, wherein R3 is a branched (C3-C5)alkyl unsubstituted or substituted with deuterium, and R4 is phenyl unsubstituted or substituted with methyl unsubstituted or substituted with deuterium.
  4. The compound according to claim 1, wherein R1 and R2, each independently, are selected from methyl, ethyl, and a branched (C3-C5)alkyl.
  5. The compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of:
    Figure PCTKR2015011888-appb-I000091
    Figure PCTKR2015011888-appb-I000092
    Figure PCTKR2015011888-appb-I000093
    Figure PCTKR2015011888-appb-I000094
    Figure PCTKR2015011888-appb-I000095
  6. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2015/011888 2014-11-06 2015-11-06 Organic electroluminescent compound and organic electroluminescent device comprising the same Ceased WO2016072780A1 (en)

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EP2053112B1 (en) * 2007-10-25 2011-08-24 Gracel Display Inc. Novel red electroluminescent compounds and organic electroluminescent device using the same

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JP2019533035A (en) * 2016-09-30 2019-11-14 ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド ORGANIC ELECTROLUMINESCENT MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE CONTAINING THE SAME
CN109715759B (en) * 2016-09-30 2023-05-12 罗门哈斯电子材料韩国有限公司 Organic electroluminescent material and organic electroluminescent device comprising the same
JP2020045340A (en) * 2018-09-20 2020-03-26 北京夏禾科技有限公司 Organic luminescent material containing novel auxiliary ligand
JP2022017297A (en) * 2018-09-20 2022-01-25 北京夏禾科技有限公司 Organic luminescent material containing a novel co-ligand
JP7011333B2 (en) 2018-09-20 2022-02-10 北京夏禾科技有限公司 Organic luminescent material containing a novel co-ligand

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