WO2012008637A1 - Composé électroluminescent bleu à base d'iridium présentant des dérivés d'acide-n-oxyde picolinique ou d'acide picolinique dissolubles utilisé en tant que ligand auxiliaire et élément électroluminescent organique à champ électrique - Google Patents

Composé électroluminescent bleu à base d'iridium présentant des dérivés d'acide-n-oxyde picolinique ou d'acide picolinique dissolubles utilisé en tant que ligand auxiliaire et élément électroluminescent organique à champ électrique Download PDF

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WO2012008637A1
WO2012008637A1 PCT/KR2010/004659 KR2010004659W WO2012008637A1 WO 2012008637 A1 WO2012008637 A1 WO 2012008637A1 KR 2010004659 W KR2010004659 W KR 2010004659W WO 2012008637 A1 WO2012008637 A1 WO 2012008637A1
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picolinic acid
light emitting
acid
oxide
layer
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PCT/KR2010/004659
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Korean (ko)
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진성호
이승준
신인애
박진수
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부산대학교 산학협력단
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Priority to PCT/KR2010/004659 priority Critical patent/WO2012008637A1/fr
Publication of WO2012008637A1 publication Critical patent/WO2012008637A1/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
    • 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

  • Iridium-based blue light emitting compound having a picolinic acid or picolinic acid-N-oxide derivative capable of solution processing as a secondary ligand and an organic light emitting device comprising the same
  • the present invention relates to a blue rhythm complex compound capable of a solution process and an organic electroluminescent device comprising the same, and more particularly to an alkyl, alkyloxyalkoxy, alkylamine or arylamine or amino so that the efficiency of the solution process can be greatly improved.
  • Blue iridium complexes having a picolinic acid or picolinic acid-N-oxide derivative having an alkylamine derivative introduced at carbon 4 of picolinic acid or picolinic acid-N-oxide as an auxiliary ligand and an organic comprising the same It relates to an electroluminescent device.
  • LCDs liquid crystal displays
  • PDPs plasma display panels
  • Conventional electroluminescent devices include inorganic semiconductors made of pn junctions such as ZnS and CdS. Inorganic electroluminescent devices using a light emitting image generated when an electric field is applied to the electric field are mainly used, but in the case of a non-family electroluminescent device, a driving voltage of 220 V or more is required, and since the device is manufactured in a vacuum state, it is difficult to increase the size. In particular, there was a problem that it is difficult to obtain high efficiency blue.
  • 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 within the organic material. It uses organic electroluminescence where energy is emitted as light. Compared with LCD, organic light emitting diodes are attracting attention as next-generation display devices because they have a good viewing angle, low power consumption, and a high response speed, which can process high quality images. Light emission from organic light emitting diodes can be classified into fluorescence and phosphorescence.
  • Organic light emitting diode including light emitting layer
  • Doped organic compounds share electrons between atomic carbon and other carbon atoms, or between atomic carbon and other atoms to form molecules through covalent bonds.
  • Orbital, Atomic Orbital (AO) is converted into molecular orbital (Molecular Orbital, M0).
  • M0 molecular orbital
  • the band formed by many coupling orbits is called a valence band
  • the die formed by many anti-bonding orbits is called a conduction band.
  • the lowest energy level of the conductive band is called LUMCKLowest Unoccupied Molecular Orbital (H0M0), and the energy difference between the energy of HOMO and LUM0 is called the band gap.
  • the injected electrons and holes recombine to form an exciton, which corresponds to the energy band gap of the light emitting layer in the process of converting the electrical energy of the exciton into light energy. Implement the light of color.
  • 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 be changed when transitioning from the excited state to the ground state. Since the ground state of the organic molecules is singlet state, the singlet axtone emits light and It can transfer to the fetus, but triplet excitons can't shine and metastasize. Therefore, in general, the maximum internal quantum efficiency of an organic light emitting diode doped with a fluorescent dye is
  • the phosphorescent organic electroluminescence device (electrophosphorescence) device that can significantly improve the luminous efficiency of the organic light emitting device is S.R. Professor Forrest and M.E. of USC.
  • the spin–orbital bond is proportional to the square of the atomic number, so the complex of heavy atoms such as platinum (Pt), iridium (Ir), europium (Eu), terbium (Tb) It is known that phosphorescence efficiency is high.
  • platinum complexes the lowest triplet excitons are ligand-centered excitons (IX excitons), while the iridium complexes have the lowest energy triplet excitons in the center of the metal-ligand charge transfer state (metal). ligand charge transfer (MLCT).
  • iridium complexes form larger spin-orbital bonds compared to platinum complexes, resulting in a much shorter triplet aciton lifetime and high phosphorescence efficiency.
  • TEZ 1 ri azo 1 e
  • UPC has announced that the green phosphorescent dopant is formed on the light emitting layer and a high luminous efficiency of 82 lm / W is achieved using a hole injection material developed by LG Chem.
  • phosphorescent organic light emitting diodes emitting green and red light have been developed, but blue phosphorescent organic light emitting diodes having excellent luminous efficiency, color coordinates, and lifetime have not been developed.
  • a material called Flrpicdridium ( ⁇ ) bis [2,2 '(4' ⁇ dif luorophenyl) ⁇ pyridinato— N, C2 '] picolinate) has been developed, but it is still not a pure blue light emitting material in terms of color purity.
  • an object of the present invention is conventional blue phosphorescent light emitting material and a UV-visible, PL and EL spectra while doing similar be solubility is significantly enhanced light-emitting layer formed by a solution process " To provide a possible iridium complex and an organic EL device by a solution process comprising the same All.
  • ⁇ represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms
  • Ar is an aryl group
  • 3 ⁇ 4 is halogen
  • 3 ⁇ 4 is hydrogen or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms
  • 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-alkylaminepicolinic acid -N-oxide, 4-arylamine picolinic acid -N-oxide, 4-aminoalkylamine picolinic Acid-N-oxide.
  • ⁇ may be an alkyl group having 1 to 10 carbon atoms
  • the aryl group may be phenyl, naphthalene, fluorene, carbazole, phenazine, or phenanthrol ine.
  • Phenanthridine acridine, cinol ine, quinazoline, quinoxal ine, naphthydrine, phthalazine , Quinolizine, indole, indazole, pyridazine, pyrazine, pyrimidine, pyridine, pyridine, pyrazole ), Imidazole, and pyrrole.
  • Ra is an alkyl group having 1 to 10 carbon atoms substituted with halogen
  • R 2 is fluorine or chlorine
  • an organic electroluminescent device in which the above-described iridium complex for a solution process is included in a light emitting layer.
  • the organic light emitting display device includes a first electrode and a second electrode formed to face the first electrode, wherein the light emitting layer is a solution process between the first electrode and the second electrode.
  • a buffer layer may be provided between the first electrode and the light emitting layer, and the electron transport layer and the electron injection layer may be further included between the light emitting layer and the second electrode.
  • the buffer layer includes a hole injection layer stacked on top of the first electrode, and a hole transport layer stacked on top of the hole injection layer,
  • the rhythm complex compound for the solution process synthesized according to the present invention is characterized by being included as a dopant of the light emitting layer.
  • the iridium complex for the solution process synthesized according to the present invention has a similar UV-visible, PL and EL spectra, the emission color and solubility are significantly improved, and can be easily dissolved in an organic solvent.
  • the light emitting area of the area can be produced.
  • the rhythm complex compound for the solution process of the present invention introduces a pyridine derivative substituted with an alkyl or alkoxy group and a phenyl derivative substituted with a halogen compound as a main ligand, and especially 4-alkoxy picolinic acid and 4-alkyloxy as an auxiliary ligand.
  • the iridium complex of the present invention may be applied to a pyridine derivative substituted with an alkyl or alkoxy group introduced into a main ligand and a phenyl derivative substituted with a halogen compound.
  • the organic solvent can be used as a light emitting material that is soluble in a general organic solvent, improves heat resistance, has excellent interface properties with electrodes, and has excellent thin film properties.
  • 1 and 2 respectively show an aryl derivative substituted with a halogen atom and a pyridine derivative having an alkyl or alkoxy substituent introduced into the main ligand, 4-alkoxypicolinic acid, 4-alkyloxyalkoxypicoli, according to an embodiment of the present invention.
  • 3 and 4 are cross-sectional views schematically showing an organic light emitting display device having a single layer and a multi-layer type to which the iridium complex for a solution process synthesized according to the present invention is applied.
  • FIG. 5 is a graph showing the results of measuring the UV-visible absorption spectrum using (dfpmpy) 2lr (E0-picN-0), which is a iridium complex for solution processing, synthesized according to an embodiment of the present invention.
  • (dfpmpy) 2 Ir (E0-picN-0) is a graph showing the results of measuring the intensity of photoluminescent (PL).
  • FIG. 7 is a graph showing electroluminescence (EL) intensity measurement results for an electroluminescent device using Flrpic, an iridium complex compound known to exhibit blue light emission, as a dopant of a light emitting layer.
  • EL electroluminescence
  • the organic light emitting display 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 terms of luminous efficiency.
  • the blue light emitting materials having such a phosphorescent property in particular, the existing blue phosphorescent rhythm complex compound and yv-visible, PL and EL spectra are similar, but the emission color and solubility are greatly improved, and the solubility is improved, so that the compatibility of the host and the like is improved.
  • An organic electroluminescent device was developed which includes an excellent solution process rhythm complex compound and solution process rhythm complex compound in a light emitting layer.
  • aromatic aryl derivatives and pyridine derivatives are introduced as main ligands, and 4-alkoxy picolinic acid, 4-alkyloxyalkoxy picolinic acid, 4-alkylamine picolinic acid, 4 as auxiliary ligands.
  • the iridium complex synthesized in the present invention has a structure of formula (1).
  • 3 ⁇ 4 is an alkyl group having a carbon number of ⁇ ⁇ 20 or an alkoxy group having 1 to 20 carbon atoms;
  • Ar is an aryl group;
  • R 2 is halogen, 3 ⁇ 4 is hydrogen or an unsubstituted or substituted 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-alkylaminepicolinic acid -N-oxide, 4-arylaminepicolinic acid -N-oxide, 4-aminoalkylaminepicolinic Acid-N-oxide.
  • the iridium complex according to the present invention is introduced into the main pyridine (main Hgand) is an aromatic pyridine derivative introduced with an alkyl or alkoxy group and an aryl derivative introduced with a halogen compound.
  • the main ligand is a main factor for determining the emission color, and in particular, the emission property may be converted according to the electron density of nitrogen (N) contained in the ligand.
  • N nitrogen
  • the aromatic aryl derivative and the pyridine derivative introduced into the main ligand according to the present invention the electron density of the nitrogen included in the structure is greatly increased compared to the conventionally developed iridium complex compound, thereby showing pure blue light emission.
  • the aryl group introduced into the main chain of the iridium complex synthesized according to the present invention includes phenyl, naphthalene, carbazole, fluorene, phenaz ine, and phenanthrene. line, phenanthr idine, acridine, cynoline, quinazoline, quinoxaline, naphthydrine, phthalazine Quinolizine, indole, indazole, pyridazine, pyrazine ⁇ !
  • ⁇ Pyrimidine, pyridine, pyridine, pyrazole ( pyrazole), imidazole (imidazole), it may include a "such as the blood (pyrrole), preferably, phenyl, naphthalene, carbazole, fluorene, etc., but are not limited the present invention thereto.
  • aromatic aryl derivatives and pyridine introduced into the main ligand according to the present invention Derivatives may be substituted with various substituents such as alkyl groups, alkoxy groups, halogens and the like.
  • the iridium complex compound synthesized according to the present invention may be commonly used in organic solvents and may improve the interfacial properties with electrodes when applied to organic electroluminescent devices.
  • substituents that may be substituted on the aromatic ring linked to pyridine are, for example, an alkyl group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, preferably having 1 to 20 carbon atoms, and preferably having 1 to 10 carbon atoms. It contains an alkoxy group.
  • halogen atoms such as fluorine (F) (chlorine (C1), bromine (Br), iodine (I) and the like may be used as substituents on the aryl ring, and preferred halogen atoms include fluorine and chlorine.
  • an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms may be introduced separately from the above-described halogen atom as the aryl ring introduced into the main ligand.
  • alkyl group which is introduced to the ring may be substituted by a halogen atom, such as, for example, fluorine, chlorine.
  • an ancillary Hgand 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 compound for the solution process of the present invention may exhibit pure blue light emission and has less conjugated structure. desirable.
  • a feature of the present invention is that the secondary ligands in various forms to improve the solubility
  • Auxiliary ligands (X) which may be selected in connection with the present invention in which a substituent is introduced include
  • 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.
  • Iridium complex compound ((7)) for solution process in which 4-aminoalkylamine picolinic acid-N-oxide was introduced into the secondary ligand can be synthesized.
  • FIG. 2 is a schematic diagram illustrating a process of synthesizing the iridium complex compound of Chemical Formula 1 according to an embodiment of the present invention.
  • an aromatic boronic acid such as a pyridine ' ((8)) derivative substituted with an alkyl or alkoxy group having 1 to 20 carbon atoms and a phenylboronic acid substituted with a halogen atom such as fluorine is K 2
  • An arylpyridine ligand ((10)) is produced by Suzuki synthesis in C0 3 with Pd (PPh 3 ) 4 and THF solvent.
  • the obtained arylpyridine ligand and iridium chloride hydrate (IrCl 3 * 3H 2 0) is dissolved in a suitable solvent and then mixed to synthesize a chloride-bridged dimer ((ll)).
  • the obtained chlorine-crosslinked dimer ((11)) has 4-chloropicolinic acid or 4-chloropicolinic acid-N-oxide, dibutylaminepicolinic acid, dibutylaminepicolinic acid-N.
  • Iridium complex compound ((12)) for solution process in which 4-aminoalkylamine picolinic acid-N-oxide is introduced into the auxiliary ligand can be synthesized. It was confirmed that the iridium complex compound synthesized through the above method exhibited a maximum emission peak from approximately 450 nm to 470 nm and thus had pure blue emission characteristics.
  • the iridium complex for the solution process synthesized through the above method is similar to the existing blue phosphorescent iridium complex and UV-visible, PL and EL spectra, and the emission color and solubility are greatly improved. For example, it is used as a dopant of the light emitting layer of the organic light emitting device.
  • FIG. 3 schematically illustrates an organic light emitting display device 1000 in a single layer type to which the above-described rhythm complexing 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 1150, and the second electrode 1180 are sequentially stacked.
  • the substrate 1100 may be made of, for example, glass or plastic and a ground material.
  • the first electrode 1110 and the second electrode 1180 for example, a portion that functions as an anode (anode) and a cathode (cathode), respectively, the first electrode 1110 is a second A material having a large work function of the electrode 1180 is used.
  • the first electrode 1110 is an effective material for injecting holes, which are positive-charged carriers, and is a metal, a mixed metal, an alloy, a metal oxide, or a mixed metal oxide or a conductive polymer. Can be.
  • the first electrode 1110 may be indium-tin oxide (IT0), fluorine doped tin oxide (FT0), Zn0-Ga 2 0 3) or Zn0-Al 2 0 3 , Sn0 2 -Sb 2 0 3
  • IT0 indium-tin oxide
  • FT0 fluorine doped tin oxide
  • Zn0-Ga 2 0 3 Zn0-Al 2 0 3
  • Sn0 2 -Sb 2 0 3 Materials such as a conductive metal oxide such as a mixed metal oxide, polyaniline, polythiophene, and the like may be used, and according to a preferred embodiment, it is IT0.
  • the second electrode 1180 is a material effective for injecting electrons, which are negative charged carriers, and includes gold, aluminum, copper, silver, or an alloy thereof; Aluminum, indium, chest, barium, magnesium and alloys thereof, such as chest / aluminum alloys, magnesium / silver alloys, aluminum / lithium alloys, and the like; Or in some cases, selected from metals belonging to rare earths, lanthanides (13111 ⁇ 31 ⁇ (16), and actinides), preferably aluminum, or aluminum / calcium alloys.
  • the above-described rhythm complex for solution processing synthesized according to the present invention is used as a dopant.
  • a host which is a luminescent material is included.
  • the host is selected so that the energy emitted from the host included in the light emitting layer 1150 can be transferred to the iridium complex compound, which is a dopant. Can be.
  • the host included in the emission layer 1150 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 blue region, may be, for example, a poly (phenylenevinylene) PPV, poly (fluorene), polyparaphenylene (! 0 ⁇ ) ⁇ 3-1) polymer materials such as 1 ⁇ 161), PPP), poly (alkyllythiophene), polypyridine, PPy, etc., and distyrylbenzene (DSB) , Distyrylbenzene derivative (PESB), distyrylarylene (DSA), distyrylarylene derivative, 1, 2, 3, 4, 5-pentaphenyl-1, 3-cyclopentadiene (1,2, Cyclopentadiene derivatives such as 3,4, 5-pent apheny 1-1, 3-cyc 1 opent ad iene (PPCP), DPVBi (4,4'-bis (2,2'-diphenyl vinyl) -l, l'-biphenyl), DPVBi derivatives, and spiro -DP
  • hosts having phosphorescent properties that can be used in connection with the present invention include aryl amines, carbazoles, and spiros.
  • 4, 4-N, N-dicarbazole-biphenyl (4, 4-N, Nd i carbazo 1 eb i pheny 1, CBP), N, N-dicarbazoyl-3, 5-benzene (N , Nd i carbazoy 1 -3, 5-benzene, mCP), poly (vinylcarbazole, PVK), polyfluorene, 4,4'-bis [9 ⁇ (3,6biphenylcarbazolyl)]-1 -1, ⁇ -biphenyl 4,4'-bis [9- (3,6-biphenylcarbazolyl)]-1 -1'1'-biphenyl, 9,10-bis [(2 ', 7'-butyl) -9', 9 ': — spirobifluorenyl anthracene,
  • the light emitting layer 1170 is laminated on top of the first electrode 1110 with a thickness of approximately 5 to 200 ⁇ , preferably 50 to 10 ran, wherein the iridium complex for the solution process synthesized according to the present invention is a dopant. It is included in the concentration of 3 to 20% by weight, preferably 5 to 10% by weight based on the light emitting layer 1170.
  • the iridium complex compound for the solution process synthesized according to the present invention, as well as the organic light emitting device 1000 in the form of a single layer described above, a multi-layered form provided with a separate layer for electron / hole transport between the light emitting layer and the electrode.
  • the organic light emitting diode 2000 includes a substrate 2100, a first electrode 2110, a hole injection layer HIL 2130, and a hole transporting layer HTL 2140.
  • a buffer layer 2120, a light emitting layer 2150, an electron transporting layer (ETL) 2160, an electron inject ion layer (EIb, 2170), and a second electrode 2180 sequentially It has a stacked form.
  • the buffer layer 2120 stacked between the first electrode 2110 and the light emitting layer 2150 may be disposed between the material used as the first electrode 2110 and the light emitting layer 2150.
  • the buffer layer 2120 may be functionally divided into a hole injection layer 2130 and a hole transport layer 2140.
  • the hole injection layer 2130 constituting the buffer layer 2120 not only improves the interfacial property between the material such as ITO used as the first electrode 2110 and the organic material used as the hole transport layer 2140. It is applied to the upper part of the surface where the surface is not flat to soften the surface of ITO, thereby improving conductivity or luminous efficiency.
  • the hole injection layer 2130 has a work function level of ⁇ 0 and a hole transport layer 2140 in order to adjust the difference between the work function level of ⁇ and the like as the first electrode 2110 and the HOMO level of the hole transfer insect 2140.
  • a material having a median value of HOMO level of a material having a particularly suitable conductivity is selected.
  • Materials for forming the hole injection layer 2120 in the present invention are copper-phth 1 a 1 ocyan i neCCuPc), N, N ' ⁇ di naphthy ⁇ - ⁇ , ⁇ ' -pheny 1 ⁇ (1 , ⁇ — bi pheny 1) ⁇ 4,4'-diamine, NPD), a-NPD, 4,4 ', 4''-tris [methylphenyl (phenyl) amino] triphenyl amine (m-MTDATA), 4,4', 4 ''-tris [l-naphthyl (phenyl) amino] triphenyl amine (l-TNATA), 4,4', 4 ' * -tris [2-naphthyl (phenyl) amino] triphenyl amine (2-TNATA), 1, 3 , Aromatic compounds such as 5- 1 ris [N- (4-di pheny 1 am i nopheny 1) phenyl amino] benzene (p-DPA
  • the hole injection layer 2130 may be coated on the first electrode 2110 to a thickness of 20-200A.
  • the hole injection layer (2130) is formed on the upper portion of the hole transport layer (2130) hole transport layer (2140) is formed so that it can be supplied to the light emitting layer 2150 stably through the hole injection layer (2130), the hole is smoothly transported, delivered
  • the material of which the HOMO level of the hole transport layer 2140 is higher than the HOMO level of the light emitting layer 2150 is selected.
  • Materials that can be used as the hole transport layer 2140 in connection with the present invention include N, N'-bis (3-methylphenyl) -N, N'-dipheny ⁇ [1, 1'-di phenyl-4, 4 ' -diamine (TPD), ⁇ -TPD, N, N'-bis (l-naphthyl N.N'-biphenyl-tl, ⁇ -biphenyl] -4,4'-diamine (TPB), N, N '-di (naph t ha 1 ene- 1-y 1) -N, N'-diphenyl-benzidene, NPB), triphenylamine (TPA), bis [4- (N, N-diethylamino) -2-methylphenyl] (4 -methylphenyl) methane (MPMP), ⁇ , ⁇ , ⁇ ', ⁇ ' -tetrakis (4-methyl phenyl)-(1, l'
  • the hole transport layer may be deposited on top of the hole injection layer 2130 with a thickness of about KKL00 nm.
  • each material used in the hole injection layer and the hole transport layer is Rather than having one function, it includes both functions.
  • the material used as the hole injection layer not only improves the hole transport or transport but also the material used as the hole transport layer also improves the hole injection.
  • the materials used in the hole injection layer and the hole transport layer can be distinguished, but such materials are only a matter of choice, and as a whole, these materials are the first electrode 2110 and the light emitting layer 2150. It is included in the buffer layer 2120.
  • the electron injection layer 2170 and the electron transfer layer 2160 which may correspond to the hole injection layer 2130 and the hole transfer layer 2140, are disposed between the light emitting layer 2150 and the second electrode 2180. Is formed.
  • the electron injection layer 2170 is used 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. And may induce doping for 2160.
  • the electron transport layer 2160 is mainly composed of a material containing a chemical component that attracts electrons, which requires high electron mobility and stably supplies electrons to the light emitting layer 2150 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.
  • Electrotransmitters that can be used according to the invention include Alq 3 and oxadizole Contains ingredients. Specifically, Tris (8-hydroxyquinolinato) aluminum (Aki3); 2, 9-dimethyl-4, 7-diphenyl-l, 10-phenanthrol ine (DDPA);
  • Azole compounds such as 3- (4-bi pheny 1) -4-pheny 1 -5- (4- 1 er t -but y 1) -1, 2, 4- 1 ri azo 1 e (TAZ); pheny lquinoza line.
  • Alq 3 was used as the electron transport layer 2160, and the electron transport layer 2160 may be stacked on the emission layer 2150 to a thickness of 5 to 150 nm.
  • HBL hole blocking layer
  • the solution process iridium complex synthesized according to the present invention exhibits a wavelength corresponding to the pure blue region.
  • the improved solution process rhythm complex compound is a conventional blue phosphor as shown in FIG. 3 (dfpmpy). 2 Ir (picN-0) and It can be seen that the UV-visible absorption spectra are very similar, and the PL spectrum of FIG.
  • reaction catalyst (2.3 g, 2 ⁇ ol) as reaction catalyst under nitrogen.
  • reaction The mixture was refluxed at 85 ° C. for 15 hours and the reaction was confirmed by TLC.
  • the mixture was cooled to room temperature, and the organic layer was extracted using diethyl ether (2 x 200 mL) and brine. Water remaining in the organic layer extracted with anhydrous magnesium sulfate (MgS0 4 ) is removed, and the magnesium sulfate containing water is filtered, and then the solvent is removed under reduced pressure.
  • MgS0 4 anhydrous magnesium sulfate
  • Example 3 Preparation of complex compound having picolinic acid-N-oxide as auxiliary ligand Chlorine-crosslinked dimer obtained in Example 2 (1.02 g, 0.8 dl ol), picolinic acid-N-oxide (0.33 g, 2.4 ⁇ ol) and Na 2 C0 3 (0.82 g, 8 ⁇ ol) are added to a 50 mL volumetric flask and 2-ethoxyethanol (20 mL) is added as a solvent and refluxed at 130 ° C for 15 to 17 hours. After completion of reaction by TLC, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the organic layer was extracted with dichloromethane (2 x 50 mL) and brine.
  • the separated organic layer was dried with anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent was removed under reduced pressure.
  • the iridium complex compound obtained through this example is abbreviated as "(dfpmpy) 2 Ir (picN-0)".
  • the separated organic layer was dried over anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent was removed under reduced pressure.
  • the rhythm complex compound obtained through this example is abbreviated as "(dFpmpy) 2 Ir (E0-picN-0)".
  • the separated organic layer was dried with anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent was removed under reduced pressure.
  • the rhythm complex compound obtained through this example is abbreviated as "(dFpmpy) 2 Ir (Bu 2 N-picN-0)".
  • Example 2 Chlorine-crosslinked dimer obtained in Example 2 (1.02 g, 0.8 cc ol), 4-chloropy Collinic acid-N-oxide (0.42 g, 2.4 'ol) and Na 2 CO 3 (0.82 g, 8' ol) were added to a 50 mL volumetric flask and l, 3-diaminopropane (20 mL) was added as a solvent. After 15-17 hours, reflux at 130 ° C. After completion of reaction by TLC, the mixture was cooled to room temperature to remove the solvent under reduced pressure, and the organic layer was extracted with dichloromethane (2 x 50 mL) and brine.
  • the separated organic layer was dried over anhydrous magnesium sulfate (MgS0 4 ), filtered, and then the solvent was removed under reduced pressure.
  • the iridium complex obtained through this example is abbreviated as "(dFpmpy) 2 Ir (H 2 N- (C3 ⁇ 4) 3N-piciH))".
  • Example 10 Preparation of Complex Compound Having Picolinic Acid-N-oxide as Secondary Ligand Chlorine-crosslinked dimer obtained in Example 8 (1.22 g, 0.8 mmol), picolinic acid-N-oxide (0.33 g, 2.4 ⁇ ol) and Na 2 CO 3 (0.82 g, 8 ⁇ ol) are added to a 50 mL volumetric flask, and 2-ethoxyethanol (20 mL) is added as a solvent and refluxed at 130 ° C for 15 to 17 hours.
  • Example 8 Chlorine-crosslinked dimer (1.22 g, 0.8 ⁇ l ol), 4-chloropicholic acid-N-oxide (0.42 g, 2.4 ⁇ l ol) and Na 2 CO 3 (0.82 g, 8 ⁇ l ol) obtained in Example 8
  • 2-ethoxyethanol (20 mL) was added as a solvent, and the mixture was refluxed at 130 ° C for 15 to 17 hours. After completion of reaction, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the organic layer was extracted with dichloromethane (2 x 50.mL) and brine.
  • the separated organic layer was dried over anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent was removed under reduced pressure.
  • Get The iridium complex obtained through this example is abbreviated as "(dFCF 3 pmpy) 2 Ir (E0-picN-0)".
  • Example 9 50 mL of chlorine-crosslinked dimer (1.02 g, 0.8 ⁇ ⁇ , 4-chloropicholic acid-N-oxide (0.42 g, 2.4 ⁇ ol) and Na2 ⁇ 3 (0.82 g, 8 mmol) obtained in Example 9 Place in a volumetric flask and add dibutylamine (20 mL) as a solvent and reflux for 15 to 17 hours at 130 ° C. Check for complete reaction by TLC, and then mix the mixture to room temperature under reduced pressure. Remove the solvent and extract the organic layer with dichloromethane (2 x 50 mL) and brine The separated organic layer is dried with anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent is removed under reduced pressure.
  • MgS0 4 anhydrous magnesium sulfate
  • Example 9 Chlorine-crosslinked dimer obtained in Example 9 (1.02 g, 0.8 mmol), 4-chloropicol Linic acid-N-oxide (0.42 g, 2.4 ⁇ ol) and Na 2 CO 3 (0.82 g, 8 mmol) were added to a 50 mL volumetric flask, and 1,3-diaminopropane (20 mL) was added as a solvent. Reflux at 130 ° C for ⁇ 17 hours. After completion of reaction by TLC, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the organic layer was extracted with dichloromethane (2 x 50 mL) and brine.
  • the separated organic layer was dried with anhydrous magnesium sulfate (MgS0 4 ), filtered, and the solvent was removed under reduced pressure.
  • the iridium complex obtained through this example is abbreviated as "(dFCF 3 pmpy) 2 Ir (H 2 N- (CH 2 ) 3 N-picN-0)".
  • rhythm complexes (dfpmpy) 2 Ir (E0-picN-0) and (dFCF 3 pmpy) 2 Ir (E0-picN-0) which are the rhythm complexes for the solution process synthesized through the processes of Examples 4 and 11, respectively.
  • An organic light emitting display device was fabricated using as a dopant for a light emitting layer.
  • a transparent electrode substrate coated with indium-tin oxide (ITO) on a glass substrate is After cleaning, the anode was coated with a photoresist resin and an etchant using the photoresist resin and an etchant to form an anode using the IT0 coated transparent electrode substrate.
  • ITO indium-tin oxide
  • the hole injection layer was coated with a polythio.pen derivative, poly (3,4-ethylenedioxythi ophene) -poly (styrene sul fonate) (PEDOT), which is a conductive polymer, to a thickness of 100 A, and then 50 minutes at 110 ° C. Baking during.
  • PEDOT poly(ethylenedioxythi ophene) -poly (styrene sul fonate)
  • NPB was vacuum deposited to a thickness of about 50 nm.
  • CBP or mCP which is widely used as a host material of the phosphorescent light emitting layer, is used as a host material of the light emitting layer, and the iridium complex of Example 4 (dfpmpy) 2 Ir (E0-picN-0 ) And (dFCF 3 pmpy) 2 Ir (E0-picN-0) of Example 11 were used as dopants for the light emitting dopant, and the concentration of the dopant was about 5-10%.
  • the light emitting layer was formed by a vacuum deposition method.
  • BCP and Alq 3 were vacuum deposited to a thickness of 20–60 nm, respectively, as the hole blocking layer and the electron transport layer.
  • the thin film was sequentially formed by vacuum deposition of LiF, which is an electron injection layer, to form an A1 electrode, which is a cathode, to fabricate an organic EL device.
  • the vacuum degree for vacuum deposition was deposited while maintaining the film at 4xl0 _6 torr or less to form a thin film.
  • the film thickness and growth rate were controlled by crystal sensor, and the emission area was 4 mirf, and the driving voltage was forward bias volt age.
  • Example 4 and Example 11 the iridium complex compounds (dfpmpy) 2 Ir (E0-picN-0) and (dFCF 3 pmpy) 2 Ir (EO—picN-0) according to the present invention were respectively used as dopants of the light emitting layer. Electro-optic characteristics of the organic light emitting diodes used were measured. Current density and luminance according to the increase of the voltage of the organic light emitting diode manufactured according to Example 14 were measured using eithley 236 Source Measurement and Minolta LS-100.
  • (dfCF 3 pmpy) 2 EL (E0-picN-0) is used as a dopant for measuring the EL intensity of the organic EL device as a result of the organic electroluminescence in which the iridium complex compound for the solution process is used as the dopant of the light emitting layer It can be seen that the device exhibits a maximum emission peak at about 456 ⁇ , which is the same as the maximum emission peak in PL, thus greatly improving blue emission characteristics.
  • FlrpicClr idium (DI) bis [2-2 ', 4'-dif luorophenyl) -pyridinato-N, C2'] picol inate) disclosed in U.S. Patent No. 6,835,469 is coated with a light emitting layer.
  • EL intensity was measured for organic electroluminescent devices using The measurement results are shown in FIG.
  • Flrpic reported as a phosphorescent compound of conventional blue light emission, exhibited a maximum emission peak at about 475 nm. It was confirmed that the blue luminescence properties and efficiency were inferior to the iridium complex compound synthesized according to the present invention.

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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 alkyles substitués par halogène et des dérivés de pyridine dans lesquels sont introduits des substituants alkyle ou alcoxy en tant que ligands principaux, et des dérivés alkyles, alkyl-oxy-alcoxy, alkylamines, allylamines ou amino alkylamines sur le quatrième carbone de l'acide picolinique ou de l'acide-N-oxyde picolinique en tant que ligands auxilliaires; et un élément électroluminescent organique à champ électrique, phosphorescent comprenant la couche électroluminescente présentant un dopant complexe d'iridium. Le complexe d'iridium dissoluble synthétisé à l'aide de ligands principaux et de ligands secondaires introduits par l'intermédiaire de l'iridium selon la présente invention présente une solubilité hautement accrue, ce qui permet la formation d'une couche électroluminescente 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'un élément par dépôt par évaporation sous vide.
PCT/KR2010/004659 2010-07-16 2010-07-16 Composé électroluminescent bleu à base d'iridium présentant des dérivés d'acide-n-oxyde picolinique ou d'acide picolinique dissolubles utilisé en tant que ligand auxiliaire et élément électroluminescent organique à champ électrique WO2012008637A1 (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
KR20100110958A (ko) * 2009-04-06 2010-10-14 부산대학교기술지주주식회사 용액공정이 가능한 피콜리닉산 또는 피콜리닉산-엔-옥사이드 유도체를 보조리간드로 갖는 이리듐계 청색 발광화합물 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
KR20100110958A (ko) * 2009-04-06 2010-10-14 부산대학교기술지주주식회사 용액공정이 가능한 피콜리닉산 또는 피콜리닉산-엔-옥사이드 유도체를 보조리간드로 갖는 이리듐계 청색 발광화합물 및 이를 포함하는 유기전계발광소자

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