WO2012008638A1 - Complexe électroluminescent à base d'iridium rouge présentant des dérivés d'acide picolinique ou d'acide-n-oxyde picolinique en tant que ligands auxiliaires et éléments électroluminescents organiques à champ électrique le comprenant - Google Patents

Complexe électroluminescent à base d'iridium rouge présentant des dérivés d'acide picolinique ou d'acide-n-oxyde picolinique en tant que ligands auxiliaires et éléments électroluminescents organiques à champ électrique le comprenant Download PDF

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WO2012008638A1
WO2012008638A1 PCT/KR2010/004660 KR2010004660W WO2012008638A1 WO 2012008638 A1 WO2012008638 A1 WO 2012008638A1 KR 2010004660 W KR2010004660 W KR 2010004660W WO 2012008638 A1 WO2012008638 A1 WO 2012008638A1
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light emitting
acid
picolinic acid
iridium complex
oxide
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Korean (ko)
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진성호
이승준
신인애
박진수
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부산대학교 산학협력단
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Publication of WO2012008638A1 publication Critical patent/WO2012008638A1/fr

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    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • C09K2211/1018—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
    • 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

  • Rhythm-based red light-emitting compound having a picolinic acid or a picolinic acid-N-oxide derivative capable of solution processing as a secondary ligand, and an electroluminescent device comprising the same
  • the present invention relates to a red rhythm complex compound capable of a solution process and an organic electroluminescent device comprising the same. More specifically, the alkyl, alkyloxyalkoxy, alkylamine, and aryl so as to significantly improve the thin film formation efficiency by the solution process.
  • Red iridium complexes in which an amine or an aminoalkyl derivative is introduced into the secondary ligand with a picolinic acid or picolinic acid-N-oxide derivative introduced at carbon number 4 of the picolinic acid or picolinic acid-N-oxide, and It relates to an organic light emitting device comprising the same.
  • electroluminescent devices have mainly used inorganic electroluminescent devices using a light emitting image generated when an electric field is applied to an inorganic semiconductor composed of p—n junctions such as ZnS and Cas, but in the case of inorganic electroluminescent devices, the driving voltage is AC 220V.
  • An organic light emitting device is a display using an organic material that emits light by itself. When an electric field is applied to an organic material, electrons and holes are transferred from the cathode and the anode, respectively, to be combined in the organic material. It uses organic electroluminescence where the energy generated is emitted as light.
  • organic light emitting diodes are attracting attention as next-generation display devices because they have a good viewing angle and low power consumption, and can improve image quality by significantly improving the response speed.
  • Light emission from organic light emitting diodes can be classified into fluorescence and phosphorescence. When fluorescence falls from a singlet excited state to an organic state, light is emitted.
  • Phosphorescence is a phenomenon in which organic molecules emit light when they fall from the triplet excited state to the ground state. This is described in detail as follows.
  • an organic compound doped in the organic EL optical device chair including a light-emitting layer is to share the electrons in the atomic state of the carbon and other on-carbon, Hogan, or between the atomic carbon and other atoms to form a molecule through a covalent bond
  • the atomic orbital (Atomic Orbital, AO) is converted into the molecular orbital (Molecular Orbital, M0).
  • M0 molecular orbital
  • two pairs of atomic orbitals in the atomic state each participate to form a bonding orbital and an antibonding orbital, respectively.
  • the band formed by many coupling orbits is called a valence band
  • the die formed by many anticoupling orbits is called a conduction band.
  • the highest energy level of the electronic device band is H0M0.
  • the highest energy level of the conductive band is called LlMXLowest Unoccupied Molecular Orbital, and the energy difference between HOMO and LUM0 is called the band gap.
  • exciton corresponds to the energy band gap of the emission layer in the process of switching to the electrical energy to light energy in the axial tone Implement the light of color. In this process, a single spin exciton with zero spin and triplet exciton with 1 spin are generated at a ratio of 1: 3.
  • the spin quantum number should not change when transitioning from excited state to ground state.
  • the ground state of the organic molecules is a singlet state, the singlet aciton can emit light and transition to the bottom state, but the triplet exciton can not light and transfer. Therefore, in general, the maximum internal quantum efficiency of an organic light emitting diode doped with a fluorescent dye is
  • the spin-orbit bond is proportional to the square of the atomic number, it is known that the complex of heavy atoms such as platinum (Pt), iridium (Ir), europium (Eu), and turbium (Tb) has high phosphorescence efficiency.
  • platinum complexes the lowest triplet excitons are ligand-centered excitons (LC excitons), while the iridium complexes have the lowest energy tritium axtones in the center of the metal-ligand charge transfer state. metal-ligand charge transfer (MLCT).
  • MLCT metal-ligand charge transfer
  • C. Adachi et al. Described bis (2-phenylpyridine) iridium (DI) acetylacetonate [(ppy) 2lr (acac)], a green phosphorescent pigment with iridium as its central metal, with 3-pheny 1-4- (1 '- napht hy 1) -5-pheny 1-1, 2, 4- 1 ri azo 1 e (TAZ) doped to produce an organic light emitting diode with a maximum luminous efficiency of 60 lm / W and a maximum internal quantum efficiency of 87% I did.
  • DI (2-phenylpyridine) iridium
  • DI acetylacetonate
  • a green phosphorescent pigment with iridium as its central metal
  • 3-pheny 1-4- (1 '- napht hy 1) -5-pheny 1-1, 2, 4- 1 ri azo 1 e (TAZ) doped to produce an organic light emitting diode with a maximum luminous
  • organic light emitting diodes have been developed, up to now, organic light emitting diodes for phosphorescence by a solution process of three primary colors having excellent luminous efficiency, color coordinates, and lifetime are not yet developed.
  • FIrpic Iridium (III) bis [2-2 ', 4'-difluorophenylpyridinato— N, C2'] picolinate, a phosphor that exhibits a blue emission color, and Ir (btp) 2 (acac), which realizes a red emission color (Iridium ( ⁇ )
  • the present invention has been proposed to solve the above problems, and the object of the present invention is that the UV-visible, PL and EL spectrum is similar to the existing red phosphorescent light emitting material capable of vacuum deposition, while the solubility is greatly improved and the solution
  • An object of the present invention is to provide an iridium complex compound capable of forming a light emitting layer by a process and an organic electroluminescent device by a solution process including the same.
  • Another object of the present invention to process in the solution luminescence spectrum, and color purity device manufacturing process, the iridium complex as the dopant in the light emitting layer for sikimeu species greatly to "compare and below provide enhanced devices.
  • a rhythm complex compound for a solution process in which carbazole derivatives and aromatic quinylone derivatives are introduced into the main ligand.
  • Solution iridium complex synthesized according to a preferred embodiment of the present invention has the structure of formula (1).
  • Ar is an aromatic ring; ! ⁇ Is hydrogen, an alkyl group (C1-C20) ⁇ alkoxy group (C1-C20), a cyanide group, a nitro group, a halogen, or a carbazole group; R 2 is hydrogen or an alkyl group having 1 to 20 carbon atoms; X is 4-alkoxy picolinic acid, 4-alkyloxyalkoxy picolinic acid, 4-alkylamine picolinic acid, 4-arylamine picolinic acid, 4-aminoalkylamine picolinic acid, 4-alkoxy picolinic acid -N-oxide, 4-alkyloxyalkoxypicolinic acid -N-oxide, 4-alkyl amine picolinic acid -N-oxide, 4-arylaminepicolinic acid -N-oxide, 4-aminoalkylamine picolinic acid -N-oxide.
  • the aromatic ring (Ar) connected to the quinoline of Formula 1 includes a phenyl group, naphthalene group, carbazole group, fluorenyl group, the functional group (Ri) substituted in the aromatic ring is 1 carbon It may be a methyl group of ⁇ 20, may be a special group having 1 to 20 carbon atoms, the halogen to be substituted may include fluorine or chlorine.
  • an organic electroluminescent device in which the iridium complex for a solution process as described above is included in the light emitting layer.
  • the organic electroluminescent device comprises, for example, a first electrode functioning as an anode. and; And a second electrode formed to face the first electrode and functioning as a cathode, wherein the light emitting layer is stacked between the first electrode and the second electrode.
  • An organic light emitting display device may have a multilayer form further comprising a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, and an electron transport layer and an electron transport layer between the light emitting layer and the second electrode.
  • the iridium complex is included in a concentration of 3-20% by weight based on the total amount of the light emitting layer, and is used as a dopant capable of interacting with other host materials.
  • the solution process iridium complex synthesized according to the present invention has a similar UV-visible, PL and EL spectra and a significant improvement in solubility compared to the known vacuum evaporation-wearing red rhythm emitting materials, and is easily dissolved in organic solvents. Therefore, a large light emitting area can be produced.
  • the iridium complex for the solution process of the present invention introduces aromatic quinoline derivatives and carbazole derivatives as main ligands, and in particular, 4-alkoxy picolinic acid, 4-alkyloxyalkoxy picolinic acid and 4-alkylaminepi as secondary ligands.
  • aromatic quinoline derivatives and carbazole derivatives as main ligands, and in particular, 4-alkoxy picolinic acid, 4-alkyloxyalkoxy picolinic acid and 4-alkylaminepi as secondary ligands.
  • a red phosphorescent organic EL device may be manufactured by using the light emitting layer as a dopant of the light emitting layer.
  • the iridium complex of the present invention can introduce various types of substituents into the aromatic quinoline derivatives and carbazole derivatives introduced into the main ligands, and are soluble in general organic solvents by introducing substituents to improve solubility in the secondary ligands.
  • the heat resistance property is improved and the interface property with the electrode is very excellent, and the thin film property can be used as a light emitting material having excellent excellent properties.
  • FIG. 1 is a semi-figure diagram schematically illustrating a mechanism for preparing an iridium complex for solution processing in which carbazole and aromatic quinoline are introduced into the main ligand according to one embodiment of the present invention
  • FIGS. 2 and 3 are cross-sectional views schematically showing a single-layer organic electroluminescent device and a multi-layered organic electroluminescent device to which the iridium complex for the solution process synthesized according to the present invention is applied, respectively;
  • FIG. 4 is a graph comparing UV-visible absorption spectrum measurement results for an iridium complex for a solution process synthesized according to an embodiment of the present invention and an iridium complex without a soluble substituent;
  • FIG. 5 is a photoluminescence of the iridium complex for the solution process synthesized in accordance with an embodiment of the present invention and the iridium complex without the soluble substituent introduced (photoluminescence, PL) graph showing strength measurement results;
  • FIG. 6 is a graph illustrating electroluminescence (EL) intensity measurement results for an electroluminescent device using Ir (btp) 2 (acac), an iridium complex compound known to exhibit red light emission, as a dopant of a light emitting layer.
  • EL electroluminescence
  • the present invention in the organic electroluminescent device, it is advantageous to use the light emitting material having the phosphorescent property rather than the light emitting material having the fluorescent property in light emission efficiency.
  • the process efficiency is improved by forming the light emitting layer by the red light emitting property and the solution process among the light emitting materials having such phosphorescence property, but also the solution process solution is excellent in solubility or compatibility with various organic solvents.
  • An organic light emitting display device including a sodium complex and an iridium complex in a light emitting layer has been developed.
  • aromatic quinoline derivatives and carbazole derivatives are introduced as main ligands, and 4-alkoxy picolinic acid, 4-alkyloxy alkoxy picolinic acid, 4-alkylamine picolinic acid, 4-arylaminepicolinic acid, 4-aminoalkylaminpicolinic acid, 4-alkoxypicolinic acid -N-oxide, 4-alkyloxyalkoxypicolinic acid -N- oxoxide, 4-alkylaminepicolinic acid- N-oxide, 4-arylaminepicolinic acid -N-oxide, 4- The introduction of aminoalkylamine picolinic acid-N-oxide allows the formation of a light emitting layer by a solution process as compared with conventionally known vacuum evaporative iridium-based light emitting materials.
  • a phosphorescent organic electroluminescent device can be manufactured.
  • the solubility, light emission spectrum, and color purity are improved to exhibit red light emission characteristics and light emission efficiency.
  • the iridium complex synthesized in the present invention has a structure of formula (1).
  • Ar is an aromatic ring
  • Rr hydrogen, an alkyl group (C1-C20), an alkoxy group (C1-C20), a cyanide group (CN), a nitro group (N02), a halogen, or a carbazole group
  • R 2 is hydrogen, an alkyl group having 1 to 20 carbon atoms
  • X is 4-alkoxy picolinic acid, 4-alkyloxyalkoxy picolinic acid, 4-alkylamine picolinic acid, 4-arylamine picolinic acid, 4-aminoalkylamine picolinic Acid, 4-alkoxy avoid collision -N- acid peroxide, _ 4 alkyloxy alkoxy avoid collision acid _ _ N-oxide, 4 _ alkylamine avoid collision acid -N- oxide, 4-arylamine avoid collision -N- acid oxides, 4-aminoalkyl aminepicolinic acid-N-oxide.
  • the iridium complex according to the present invention is an aromatic quinoline derivative and a carbazole derivative are introduced as a main ligand.
  • the ligand may be converted in particular depending on the electron density of nitrogen (N) contained in the ligand.
  • N nitrogen
  • the electron density of nitrogen contained in the structure is significantly increased as compared with the conventionally developed rhythm complex compound, thereby showing pure red light emission. .
  • Aromatic rings (Ar) which may be connected to quinoline in connection with the present invention include phenyl, naphthalene, carbazole, fluorene, phenazine, phenanthrol ine), phenanthridine, permidine, acridine, acridine, cinol ine, quinazoline, quinoxaline, naphthydrine , Phtalazine ⁇ quinolizine, indole, indazole, pyridazine, pyrazine, pyrimidine, pyridine, pyridine pyridine, pyrazole, imidazole, pyrrole, etc., preferably Preferably phenyl, naphthalene, carbazole, fluorene.
  • the aromatic quinoline derivatives and carbazole derivatives introduced into the main ligand according to the present invention can be substituted by various kinds of dehydration such as alkyl group, alkoxy group, cyanide group, nitro group, halogen, etc. It can be used in, and when applied to the organic light emitting device can improve the interface characteristics with the electrode.
  • a substituent which may be ' substituted ' to an aromatic ring connected to quinoline for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and preferably 1 to 20 carbon atoms It contains -10 alkoxy groups.
  • halogens such as fluorine (F), chlorine (C1), bromine (Br), iodine (I) and the like may be used as substituents on the aromatic ring connected to quinoline, and preferred halogen atoms include fluorine and chlorine.
  • a functional group () which may be substituted with an aromatic quinoline derivative and a carbazole derivative introduced into a iridium complex of an iridium complex is hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. to be. Due to the alkyl group which may be substituted for carbazole, the solubility or compatibility of the rhythm complex compound according to the present invention to the organic solvent may be improved.
  • an ancillary ligand is introduced separately from the above-described main ligand.
  • Auxiliary ligands are selected to adjust the fine color in the luminescence properties of the synthesized complex compounds.
  • the iridium complex for the solution process of the present invention may exhibit more pure red luminescence. And less conjugated structure is preferred.
  • the secondary ligand () which can be selected in connection with the present invention in which various types of substituents are introduced into the secondary ligand to improve solubility.
  • FIG. 1 is a half-figure diagram schematically illustrating a process of synthesizing the iridium complex of Chemical Formula 1 according to an embodiment of the present invention.
  • the aromatic ring has two or more rooms such as naphthalene, carbazole, fluorene, and the like.
  • the amino quinone substituted by the aromatic ring can be synthesized through the procedure of Scheme 2 below. Banungsik 2
  • Ri alkyl, alkoxy, GN, NO2, halogen, carbazole
  • the rhythm complex compound synthesized by the method showed a maximum emission peak at approximately 595 ran as shown in the emission measurement result of FIG.
  • the red iridium complex for the solution process synthesized by the above-described method has similar solubility and UV-visible, PL and EL spectra and similar solubility and improved solubility. When used as a dopant, pure red light emission can be obtained.
  • An organic light emitting diode to which an iridium complex compound synthesized according to the present invention can be applied will be described.
  • FIG. 2 schematically illustrates an organic light emitting display device 1000 in a single layer type to which the above-described rhythm complex compound may be applied according to an embodiment of the present invention.
  • the single layer organic light emitting diode 1000 has a structure in which the substrate 1100, the first electrode 1110, the light emitting layer 1140, and the second electrode 1170 are sequentially stacked.
  • the substrate 1100 may be made of a material such as, for example, glass or plastic.
  • the first electrode 1110 and the second electrode 1170 for example, a portion that functions as an anode (anode) and a cathode (cathode), respectively, the first electrode 1110 is one of the second electrode 1170 Use a material with a large work function.
  • the first electrode 1110 is an effective material for injecting a hole that is a positive-charged carrier, and is a metal, a mixed metal, an alloy, a metal oxide, or a mixed metal oxide or conductive material. It may be a polymer.
  • the first electrode 1110 includes a complex metal oxide such as ⁇ indium—tin oxide (FT0), Fluorine doped tin oxide (FT0), ⁇ or Zn0-Al 2 0 3 , Sn0 2 -Sb 2 0 3 , and polyaniline.
  • FT0 indium—tin oxide
  • FT0 Fluorine doped tin oxide
  • Zn0-Al 2 0 3 ⁇ or Zn0-Al 2 0 3
  • Sn0 2 -Sb 2 0 3 ⁇ or Zn0-Al 2 0 3
  • Sn0 2 -Sb 2 0 3 ⁇ or Zn0-Al 2 0 3
  • Sn0 2 -Sb 2 0 3 ⁇ or Zn0-Al 2 0 3
  • Sn0 2 -Sb 2 0 3 polyaniline
  • IT0 polyaniline
  • the second electrode 1170 is a material effective for injecting electrons, which are negative-charged carriers, as gold, aluminum, copper, silver, or alloys thereof; Aluminum, sulphate, barium, barium, magnesium and alloys thereof, such as calcium / aluminum alloys, magnesium / silver alloys, aluminum / lithium alloys, and the like; Or in some cases it may be selected from metals belonging to the rare earth lanthanides, actinides, preferably aluminum, or aluminum / calm alloys.
  • the above-described iridium complex for a solution process synthesized according to the present invention is used as a dopant.
  • the light emitting layer 1140 includes a host, which is a light emitting material, to increase luminous efficiency by suppressing energy loss processes such as color purity change and quenching.
  • a host which is a light emitting material
  • the host is selected so that the energy emitted from the host included in the light emitting layer 1140 can be transferred to the iridium complex compound, which is a dopant.
  • the host included in the light emitting layer 1140 may include both a host having a fluorescent property and a host having a phosphorescent property, but preferably a host having a phosphorescent property.
  • the host which is a light emitting material in the red region, may be, for example, a poly (phenylenevinylene), PPV, polyfluorene, or polyparaphenylene. ), PPP) based, poly (alkyllythiophene) based, polypyridine ( ) 0 ⁇ ( ⁇ 116) , ??
  • Polymer water such as) Vagina, distyrylbenzene (DSB), distyrylbenzene derivative (PESB), distyryl arylene (DSA), distyryl arylene derivative, 1,2,3,4,5-pentaphenyl-1 Cyclopentadiene derivatives such as, 3-cyclopentadiene (l, 2,3,4,5-pentapheny l, 3-cyclopentacliene, PPCP), DPVBi (4,4 , -bis (2,2 , -diphenyl vinyl ) -l.l'-biphenyl), DPVBi derivatives, spiro -DPVBi, and the like.
  • the light emitting layer 1170 is stacked on top of the first electrode 1110 with a thickness of approximately 5 to 200 ⁇ , preferably 50-10 nm, wherein the iridium complex synthesized according to the present invention is a light emitting layer as a dopant. It is included in the concentration of 3 to 20% by weight, preferably 5 to 10 weight 3 ⁇ 4 with respect to (1170).
  • the iridium complex synthesized according to the present invention is an organic field of the above-described monolayer form
  • the light emitting device 1000 may be applied to the organic light emitting device having a multi-layered structure in which a separate layer for electron / hole transport is provided between the light emitting layer and the electrode, and FIG.
  • the organic light emitting diode 2000 may include a substrate 2100, a first electrode 2110, a hole injection layer HIL 2120, a hole transporting layer HTL 2130, and the like. ), A light emitting layer 2140, an electron transporting layer (ETL 2150), an electron injection layer (EIL 2160), and a second electrode 2170 are sequentially stacked.
  • the hole injection layer 2120 stacked between the first electrode 2110 and the light emitting layer 2140 is an ITO used as the first electrode 2100.
  • the hole injection layer 2120 has a work function level of ⁇ 0 and a hole transport layer 2130 to control the difference between the work function level of ITO and the H0M0 level of the hole transport layer 2130 that can be used as the first electrode 2110_.
  • a material having an appropriate conductivity is selected as a material having an intermediate value of the H0M0 level of C.
  • a material forming the crystallization layer 2120 includes copper phthlalocyanine (CuPc), ⁇ , ⁇ '- dinaphthy 1-N, N'-phenyl- (l, l'-biphenyl) -4, 4'-diamine, NPD), 4,4 ', 4'tris [methyl phenyl (phenyl) amino] triphenyl amine ( m-MTDATA), 4,4 ', 4'-1 ris [1-napht hy 1 (pheny 1) am i no] triphenyl amine (l-TNATA),
  • Aromatic amines such as benzene (-DPA-TDAB) and polythiophene derivative as a conductive polymer 3,4-ethylenedioxythiophene) -poly (styrnesulfonate) (PED0T) can be used, in the embodiment of the present invention was used PED0T.
  • the hole injection layer 2120 may be coated on the upper portion of the first electrode 2110 to a thickness of 20-200A.
  • a hole transport layer 2130 to stably supply the holes introduced through the hole injection layer 2120 to the light emitting layer 2140, the hole is smoothly transported, delivered In order to ensure that the HOMO level of the hole transport layer 2130 is higher than the H0M0 level of the light emitting layer 2140 is selected.
  • Materials that can be used in the hole transport layer 2130 in connection with the present invention include
  • N'-tetrakis (4-methyl phenyl)-(1, l'-bi pheny) -4, 4-di ami ne (TTB), N, N'-bis (4-methyl phenyl
  • TTB 4-di ami ne
  • Low molecular hole transport materials such as) -N, N '-bi s (4-ethylpheny 1)-[1,1'-(3, 3 '-dimethyl) bi pheny l] -4,4'-diamine (ETPD) and; Polyvinylcarbazole, Paul Polymeric hole transport materials such as lianiline, (phenylmenyl) polysilane, etc. may be used.
  • NPB is used as the hole transport layer 2130, and the hole injection layer 2130 may be deposited on the hole injection layer 2120 to a thickness of about 10 to 100 ran.
  • an electron injection layer 2160 and an electron transport layer 2150 that can be spaced between the light emitting layer 2140 and the second electrode 2170 are provided in the hole injection layer 2120 and the hole transport layer 2130. Is formed.
  • the electron injection layer 2160 is intended to induce smooth electron injection.
  • an alkali metal or alkaline earth metal ion form is used, such as LiF, BaF 2> CsF, and the like. May be configured to induce doping to the transport layer 2150.
  • the electron transport layer 2150 is mainly composed of a material containing a chemical component that attracts electrons, for this purpose, high electron mobility is required, and stably supplies electrons to the light emitting layer 2140 through smooth electron transport. At this time, particularly strong electron-receiver components can quench electrons, so it is preferable to use an appropriate electron-receiving component to improve electron mobility.
  • Alq 3 and oxadizole components, specifically Tr is (8-hydr oxyqu i no 1 inato) aluminum (Alq3);
  • Azole compound such as 3- (4-biphenyl) -4-pheny ⁇ 5- (4-tert-butyl) -l, 2,4-triazoleCAZ) water; phenylquinozaline and the like.
  • Alq 3 was used as the electron transport layer 2150, and the electron transport layer 2150 may be stacked on the emission layer 2140 with a thickness of 5 to 150 ran.
  • HBL hole blocking layer
  • Materials that can be used for the hole blocking layer in the context of the present invention include 2,9-dimethyl-4,7-diphenyl-l, 10-phenanthronne (BCP), and the light emitting layer (2140) with a thickness of approximately 5-150 ran It may be deposited on top of).
  • the solution process iridium complex synthesized according to the present invention exhibits a wavelength corresponding to the pure red region, and thus the solution solution iridium complex (Et-CVz-PhQ) 2lr (E0-pic-N -0) shows that the existing red phosphorescent material (Et-CVz-PhQ) 2 Ir (pic-N-0) and UV-visible absorption spectrum and PL spectrum which do not have soluble substituents introduced into the secondary ligand as shown in FIG.
  • the PL spectrum of Figure 4 is also the existing red iridium complex (Et-CVz-PhQ) 2 Ir (pic-N-0) and the iridium complex for the solution process developed in the present invention, (Et-CVz It was confirmed that the PL spectrum of -PhQ) 2 Ir (E0-pic-N-0) showed luminescence in the same red region.
  • the solubility was increased, but the electrical properties were not significantly changed, compared to the organic light emitting device manufactured by vacuum deposition.
  • Example 1 Synthesis of an rhythm complex having a main ligand of ethylcarbazole-phenylquinoline and a secondary ligand of aryloxyethoxy picolinic acid
  • the organic layer containing the product was dried using magnesium sulfate, separated by column chromatography using nucleic acid and ethyl acetate, and then 1- (9-ethylcarbazole-3day) -ethanone (l- (9- Ethylcarbazole-3-yl) -ethanone (FIG. 1 (2)) 3.0 g (yield 49) was obtained.
  • the NMR results for the obtained composites are shown below.
  • Example 2 According to the same procedure as in Example 1, except that 4-chloropicolinic acid N-oxide was used in the same molar ratio instead of 4-chloropicolinic acid as an auxiliary ligand, the ethyloxypicolinic acid-N- Iridium complexes in which oxides were introduced into the secondary ligands were synthesized.
  • the iridium complex obtained through this example is abbreviated as "(Et-CVz-PhQ) 2lr (E0-pic-N-0xide)".
  • the melting point of the iridium complex compound obtained according to the present example was 185 to 210 ° C., and the NMR results are shown below.
  • Example 3 Synthesis of an Erythral Complex Having Ethyl Carbazole-Phenylquinoline Jurand and Dibutylamine Picolinic Acid
  • dibutylaminepicolinic acid is introduced into the secondary ligand according to the same procedure as in Example 1, except that 4-chloropicolinic acid is used as the auxiliary ligand in the same molar ratio and 12 ml of dibutylamine is added.
  • Synthesized iridium complex was synthesized.
  • the iridium complex obtained through the present example is abbreviated as "(Et-CVz-PhQ) 2lr (Bu2N-pic)".
  • the melting point of the iridium complex obtained in this example was 198-225 ° C.
  • the NMR results are shown below.
  • auxiliary ligand in the present embodiment in the present embodiment, 4-chloropicolinic acid N-oxaad was used in the same molar ratio instead of 4-chloropicolinic acid as an auxiliary ligand, except that 12 ml of dibutylamine was added.
  • a rhythm complex compound in which dibutylaminepicolinic acid-N-oxide was introduced into a secondary ligand was synthesized.
  • the iridium complex obtained through the present example is abbreviated as "(Et-CVz-PhQ) 2lr (Bu 2 N-pic-N-oxide)".
  • the melting point of the iridium complex compound obtained according to the present example was 200 to 220 X.
  • the auxiliary ligand is aminopropylamine picolinic according to the same procedure as in Example 1 except that 4-chloropicolinic acid is used in the same molar ratio and 12 ml of 1,3-diaminopropane is added.
  • Iridium complexes in which acid was introduced into the secondary ligand were synthesized.
  • the rhythm complex compound obtained through the present example is abbreviated as "(Et-CVz-PhQ) 2 Ir (H 2 N (CH 2) 3 N-pic-N-oxide)".
  • the melting point of the rhythm complex compound obtained according to the present example was 193 ⁇ 235 ° C, NMR results are shown below.
  • Iridium complexes in which aminopropylaminepicolinic acid-N-oxide was introduced into the secondary ligand were prepared according to the same procedure as in Example 1.
  • the iridium complex obtained through this example is abbreviated as "(Et-CVz-PhQ) 2 Ir (H2N (CH2) 3 N-pic-N-oxide)".
  • the melting point of the iridium complex obtained in this example was 190-210 ° C.
  • the NMR results are shown below.
  • the iridium complex was synthesized by repeating the same procedure as in Example 1, except that octylcarbazole was used instead of ethyl carbazole as a starting material having carbazole introduced into the main ligand.
  • the iridium complex was synthesized by repeating the same conditions and procedures as in Example 3, except that 4-chloropicolinic acid-N-oxide was introduced as an auxiliary ligand.
  • Chlorine-crosslinked dimer produced in the middle of the process of Example 3 ((5) of FIG. 1) 80 mg (0.034 ⁇ 0 1), 4-chloropicolinic acid-N-oxide 15.6 mg (0.09 ⁇ ol 1 mL of 2-ethoxyethanol was added thereto, and the mixture was refluxed for 20 hours.
  • 4-chloropicolinic acid is used as the auxiliary ligand in the same molar ratio.
  • An iridium complex in which dibutylaminopicolinic acid was introduced into the secondary ligand was synthesized according to the same procedure as in Example 1 except that 12 ml of high dibutylamine was added.
  • the iridium complex compound obtained through this Example is abbreviated as "(Octy 'CVz-PhQ) 2 Ir (Bu 2 N-pic)".
  • the melting point of the iridium complex obtained in this example was 145 ⁇ 147 ° C, NMR results are shown below.
  • Dibutylaminepicolinic acid-N according to the same procedure as in Example 1, except that 4-chloropicolinic acid-N-oxide was used as an auxiliary ligand in the same molar ratio and 12 ml of dibutylamine was added.
  • An iridium complex in which -oxide was introduced as a secondary ligand was synthesized.
  • the ' iridium complex compound obtained through the present embodiment is abbreviated as "(0ctyl-CVz-PhQ) 2lr (Bu 2 N-pic)”. Melting point of the rhythm complex compound obtained according to this Example was 145 ⁇ L47 ° C., NMR results are shown below.
  • the auxiliary ligand is aminopropylamine picolinic according to the same procedure as in Example 1, except that 4-chloropicolinic acid is used in the same molar ratio and 12 ml of 1,2-diaminopropane are added.
  • Iridium complexes in which acid was introduced into the secondary ligand were synthesized.
  • petting complex obtained through the present embodiment will be abbreviated as "(0ctyl-CVz-PhQ) 2 Ir (H2N (CH 2) 3N-pic)".
  • the melting point of the "petting complex obtained according to the present embodiment was 153 ⁇ 160 ° C, it is shown for the NMR results.
  • auxiliary ligands were used in the same manner as in Example 1 except that 4-chloropicolinic acid-N-oxide was used in the same molar ratio and 12 ml of 1,3-diaminopropane was added.
  • an rhythm complex compound in which aminopropylaminepicolinic acid-N-oxide was introduced as a secondary ligand was synthesized.
  • the iridium complex obtained through this example is abbreviated as "(Octy 'CVz-PhQ) 2 Ir (H 2 N (CH 2 ) 3 N-pic)".
  • the melting point of the iridium complex compound obtained according to the present example was 153 ⁇ 160 ° C., NMR results are shown below.
  • the soluble substituent synthesized through the process of Example 2 (Et-CVz-PhQ) 2 Ir (E0-pic-N-0xide) and a soluble substituent, which are iridium complexes for solution processing introduced into the bovine cooking gangue UV-visible hop number spectrum was measured using a Shimadzu UV-3100 spectrometer in a state in which (Et—CVz-PhQ) 2 Ir (pic-N_0xide) luminescent material was not dissolved in chloroform.
  • Example 3 is an iridium complex synthesized in Example 2 (Et-CVz-PhQ) 2 Ir (EO-pic-iH) xide) and (Et-CVz-PhQ) 2 Ir (pic-N-0xide) light emitting material It is a graph showing the results of UV-visible absorption spectrum measurement for. Looking at the UV absorption peak of the iridium complex synthesized according to the present invention, the transition phenomenon of phenylquinoline and carbazole derivatives occurs at a wavelength of about 247, 298 nm, a single term at a wavelength of about 371-571 nm It can be seen that the charge transfer state between the center metal and the ligand of the triplet occurs.
  • red iridium complex (Et-CVz-PhQ) 2 Ir (E0-pic-N— Oxide) synthesized for the solution process is the conventional red rhythm complex (Et-CVz-PhQ) 2 Ir (pic — Shows the same absorption spectrum as N-Oxide).
  • Et-CVz-PhQ red iridium complex
  • Ir E0-pic-N— Oxide
  • PL photo luminescence
  • the soluble substituent synthesized through the process of Example 2 (Et-CVz-PhQ) 2 Ir (E0-pic-N-0xide) and soluble, which is the rhythm complex for the solution process introduced into the bovine cooking gangue PL was measured with Hitachi F-4500 in a state in which a (Et-CVz-PhQ) 2 Ir (pic-N-Oxide) luminescent material in which no substituent was introduced into the secondary ligand was dissolved in chloroform.
  • PL was measured using the maximum UV wavelength measured by each iridium-based light emitting material as the excitation wavelength.
  • Example 4 is an iridium complex synthesized in Example 2 (Et-CVz-PhQ) 2 Ir (E0-pic-iH) xide) and (Et-CVz-PhQ) 2 Ir (pic-N-0xide) light emitting material
  • the PL measurement results for the graph are shown.
  • the rhythm complex compound synthesized according to the embodiment of the present invention can be seen that the maximum emission peak is formed at approximately 595nm, showing a pure red emission color.
  • the red rhythm complex (Et-CVz-PhQ) 2 Ir (E0-pic-N-0xide) synthesized for the solution process is the conventional red rhythm complex (Et-CVz-PhQ) 2lr ( The same photoluminescence spectrum as pic-N "0xide) is shown.
  • Ir (btp) 2 (acac) Iridium ( ⁇ ) bis (2- (2 ') disclosed in U.S. Patent Nos. 7, 250 and 512.

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Abstract

L'invention concerne un complexe d'iridium qui peut former un revêtement mince par dissolution d'une couche électroluminescente dans laquelle sont introduits des dérivés carbazoles et des dérivés de quinoline aromatiques en tant que ligands principaux, et des dérivés alcoxy, alkyl-oxy alcoxy, alkylamines, allylamines ou amino alkylamines sur le quatrième atome de carbone d'acide picolinique ou d'aide-N-oxyde picolinique en tant que ligands auxiliaires, et un élément électroluminescent organique à champ électrique, phosphorescent, rouge, comprenant la couche électroluminescente présentant un dopant composé de complexe d'iridium. Le complexe d'iridium dissoluble synthétisé à l'aide de ligands principaux et de ligands auxiliaires introduits par l'intermédiaire de l'iridium selon la présente invention présente une solubilité hautement accrue, ce qui permet la formation d'une couche électroluminescent par dissolution à la place d'un dépôt par évaporation sous vide, le dopage du complexe d'iridium sur la couche électroluminescente, de manière à permettre non seulement son changement d'échelle, mais également la formation d'un élément présentant une efficacité du procédé de préparation beaucoup plus importante que celle du procédé classique de préparation d'élément par dépôt par évaporation sous vide.
PCT/KR2010/004660 2010-07-16 2010-07-16 Complexe électroluminescent à base d'iridium rouge présentant des dérivés d'acide picolinique ou d'acide-n-oxyde picolinique en tant que ligands auxiliaires et éléments électroluminescents organiques à champ électrique le comprenant WO2012008638A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
WO2007042474A2 (fr) * 2005-10-07 2007-04-19 Solvay (Société Anonyme) Materiau electroluminescent
KR20080044154A (ko) * 2006-11-15 2008-05-20 부산대학교 산학협력단 발광 특성이 개선된 이리듐 착화합물 및 이를 포함하는유기전계발광소자
KR20080057377A (ko) * 2006-12-20 2008-06-25 부산대학교 산학협력단 발광 특성이 개선된 이리듐계 착화합물 및 이를 포함하는유기전계발광소자
KR20090111042A (ko) * 2008-04-21 2009-10-26 부산대학교 산학협력단 피콜리닉산-엔-옥사이드를 보조리간드로 갖는 이리듐계발광화합물 및 이를 포함하는 유기전계발광소자
KR20100110959A (ko) * 2009-04-06 2010-10-14 부산대학교기술지주주식회사 용액공정이 가능한 피콜리닉산 또는 피콜리닉산-엔-옥사이드 유도체를 보조리간드로 갖는 이리듐계 착화합물 및 이를 포함하는 유기전계발광소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007042474A2 (fr) * 2005-10-07 2007-04-19 Solvay (Société Anonyme) Materiau electroluminescent
KR20080044154A (ko) * 2006-11-15 2008-05-20 부산대학교 산학협력단 발광 특성이 개선된 이리듐 착화합물 및 이를 포함하는유기전계발광소자
KR20080057377A (ko) * 2006-12-20 2008-06-25 부산대학교 산학협력단 발광 특성이 개선된 이리듐계 착화합물 및 이를 포함하는유기전계발광소자
KR20090111042A (ko) * 2008-04-21 2009-10-26 부산대학교 산학협력단 피콜리닉산-엔-옥사이드를 보조리간드로 갖는 이리듐계발광화합물 및 이를 포함하는 유기전계발광소자
KR20100110959A (ko) * 2009-04-06 2010-10-14 부산대학교기술지주주식회사 용액공정이 가능한 피콜리닉산 또는 피콜리닉산-엔-옥사이드 유도체를 보조리간드로 갖는 이리듐계 착화합물 및 이를 포함하는 유기전계발광소자

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