WO2003092334A1 - Compose polymere phosphorescent, matiere emettant de la lumiere et dispositif organique electroluminescent (el) dote de ce compose - Google Patents

Compose polymere phosphorescent, matiere emettant de la lumiere et dispositif organique electroluminescent (el) dote de ce compose Download PDF

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WO2003092334A1
WO2003092334A1 PCT/JP2003/005352 JP0305352W WO03092334A1 WO 2003092334 A1 WO2003092334 A1 WO 2003092334A1 JP 0305352 W JP0305352 W JP 0305352W WO 03092334 A1 WO03092334 A1 WO 03092334A1
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phosphorescent
organic
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polymer compound
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Shizuo Tokito
Koro Shirane
Motoaki Kamachi
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Nippon Hoso Kyokai
Showa Denko K.K.
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Priority claimed from JP2002126731A external-priority patent/JP2003321546A/ja
Application filed by Nippon Hoso Kyokai, Showa Denko K.K. filed Critical Nippon Hoso Kyokai
Priority to AU2003231528A priority Critical patent/AU2003231528A1/en
Publication of WO2003092334A1 publication Critical patent/WO2003092334A1/fr

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Definitions

  • the present invention relates to a phosphorescent polymer compound, light emitting material and organic electroluminescent (EL) device using the compound.
  • TAn organic electroluminescent (EL) device is a device having a sandwich structure where a thin organic film containing fluorescent organic compound or phosphorescent organic compound exists between a cathode andan anode .
  • excitation of organic molecules is generated (formation of exciton) by injecting holes and electrons into the thin organic film to recombine the charges, and light (fluorescence/phosphorescence) is emitted when the excited state moves back to the ground state.
  • the organic EL device is advantageous in that light luminance of 10000 cd/m 2 or higher is achieved by applying a low voltage of approximately 10V, and that selective use of organic polymer enables emission of light from red to blue.
  • Organic EL device being self-luminous and not angle-dependent, enables a wide field of view and display with excellent visibility. Expectations are placed on organic EL device as leading candidates for future full-color displays.
  • the simplest organic EL device has a structure where a light-emitting layer is sandwichedbetween an anode and a cathode.
  • a typical type of the organic EL device contains a triple-layer structure where an electron-transporting layer is inserted between one electrode and the light emitting layer and an hole-transporting layer is inserted between the other electrode and the light emitting layer .
  • Organic molecules are excited in two states, singlet state and triplet state. In the case of electrical excitation, the generation ratio of singlet excitation to triplet excitation is 0.25:0.75. It is generally said that fluorescence is emitted from the singlet excited state and phosphorescence is emitted from the triplet excited state. Generally, deactivation from the triplet excited state occurs in a non-radiation process without light-emission.
  • the maximum quantum efficiency is as lowas 5% inanorganicEL deviceusinga fluorescent organic compound.
  • the high generation ratio (0.75) of the triplet excited state as described above there can be expected emission efficiency three times higher than fluorescent emission.
  • the organic compound contains metal complex having platinum or iridium in the center of the chemical structure thereof as phosphorescent compound, and the phosphorescent compound is doped to several-percent concentration into a host layer of carbazole or triazole compound.
  • Highly efficient emission as high as 20% has been achieved by an ingenious configuration of the device, attracting attention as a measure for attaining ultrahigh efficiency of emission.
  • polymer organic EL device which is expected to be advantageous for larger display panel, higher definition and cost reduction.
  • Polymer being soluble in organic solvents and the like, can be applicable in coating methods using polymer in form of solution, such as spin coating method, printing method and ink jet method.
  • spin coating method a coating method using polymer in form of solution
  • printing method a printing method
  • ink jet method is attracting more attention as a promising measure for display production.
  • light emittingmechanismdetermining light emission efficiency is assumed to be based on energy transfer from the singlet and triplet excited states of polyvinylcarbazole to the phosphorescent compound, or direct excitationby electron-hole recombination on molecules of the phosphorescent compound. In either event, in order for the phosphorescent compound to emit light with high efficiency, it is important that energy level of the host material in singlet and triplet excited states is high as compared to that of the phosphorescent compound, and the band gap is large.
  • EL device in order to solve a problem that low molecular weight material dispersed in host material is segregated or phase-separated, a polymer-base light-emitting material having a long-lasting stability is desired.
  • the present invention has been accomplished from the viewpoint of the above-mentioned problems, and one of the objects of the invention is to provide an organic polymer compound for use in organic EL device, having excellent stability, which enables phosphorescence emissionwith super high efficiency, especially in blue phosphorescent light emission.
  • Another object of the invention is toprovide alight emitting material, organic electroluminescent (EL) device and display apparatus using the organic polymer compound.
  • EL organic electroluminescent
  • polysilane silicone-base polymer
  • Polysilane is a polymer comprising ⁇ -conjugated silicon one-dimensional chain as a main chain structure and substituents such as alkyl group and aryl group on side chains.
  • Polysilane due to its electron systemunder quasi-one-dimensional conditions where the electrons are delocalized along the silicone one-dimensional chain, exhibits a high hole mobility on the order as high as 10 "4 cm/Vs . This value is higher by two orders of magnitude than the mobility value of polyvinylcarbazole.
  • polysilane emits near-ultraviolet light based on its quasi-one-dimensional exciton. This means that polysilane has a large band gap.
  • the electronic structure is changeable to a substituent structure as shown (3-1) to (3-3) below.
  • the band gap of poly (dibutylsilane) (hereinafter sometimes abbreviated as ⁇ PDBS") is 5.3eV while that of poly (bis (4-butylphenyl) silane) (hereinafter sometimes abbreviated as "PBPS”) is 4 eV.
  • Energy levels of the conducting band (corresponding to the lowest unoccupied molecular orbital) and valence band (corresponding to the highest occupied molecular orbital) varies depending on the band gap values.
  • Polysilane, whose side chain can be readily substituted, allows a high degree of freedom in molecular design.
  • polysilane is soluble in organic solvent and the solution can be used for forming a film on a substrate by a coating method, use of polysilane can be advantageous for fabricating large area display device.
  • the present inventors have invented a novel phosphorescent polymer compound by introducing a chemical structural unit having phosphorescent property into polymer chain of silicone-base polymer (polysilane) . That is, the present invention relates to:
  • a phosphorescent polymer compound comprising a phosphorescent unit having phosphorescent property and a repeating unit represented by formula (1) :
  • X 1 andX 2 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a cyano group, a carboxyl group, a carbonyl group, a hydroxyl group, an aryl group which may be substituted, an aryloxy group which may be substituted or a heteroaryl group which may be substituted, 2.
  • X 3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a cyano group, a carboxyl group, a carbonyl group, a hydroxyl group, an aryl group which may be substituted, an aryloxy group which may be substituted, or a heteroaryl group which may be substituted, and A represents an organic phosphorescent group,
  • a light-emitting material comprising the phosphorescent polymer compound as described in any one of items 1 to 6 above, 8. the light-emitting material as described in item 7 above, which further contains an organic compound having electron transporting property,
  • an organic electroluminescent (EL) device comprising one or more organic polymer layers between an anode and a cathode, wherein at least one of the organic polymer layers comprises the light-emitting material as described in item 7 or 8 above, 10. the organic EL device as described in item 9 above, wherein the anode is formed on a plastic substrate, 11. the organic EL device as described in item 9 or 10 above, having the organic polymer layer (s) formed by a coating method, and
  • an active-matrix display apparatus comprising the organic EL device as described in any one of items 9 to 11 above and a thin film transistor.
  • Phosphorescent polymer compound comprising a phosphorescent unit as a repeating unit emitting phosphorescent light and a repeating unit represented by formula (1) below:
  • X 1 and X 2 each represent independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, cyano group, a carboxyl group, a carbonyl group, a hydroxyl group, an aryl group, an aryloxy group, or a heteroalyl group.
  • the halogen atom represented by X 1 and X 2 is fluorine, chlorine, bromine or iodine.
  • the alkyl group represented by X 1 and X 2 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • Examples of the alkyl group include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl and cyclohexyl .
  • the alkoxy group represented by X 1 and X 2 preferably has 1 to 20 carbon atoms, morepreferably 1 to 12 carbon atoms .
  • Examples of the alkoxy group include methoxy, ethoxy, iso-propoxy and tert-butoxy.
  • the aryl group represented by X 1 and X 2 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Examples of the aryl group include phenyl, naphtyl, anthracenyl andpyrenyl .
  • the aryloxy group represented by X 1 and X 2 preferably has 6 to 30 carbon atoms, morepreferably 6 to 20 carbon atoms. Examples of the aryl group include phenyloxy, naphtyloxy, anthracenyloxy and pyrenyloxy.
  • the hetero aryl group represented by X 1 and X 2 preferably contains at least one of oxygen atom, a nitrogen atom and a sulfur atom, and preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms.
  • Examples of the hetero aryl group include imidazoryl, pyridyl, furyl, pyperidyl, benzoxazoryl, thienyl, triazoryl and carbazoryl.
  • Thephosphorescent polymer compound of thepresent invention has a copolymer structure as described above, and is hereinafter sometimes simply referred to as "copolymer".
  • Thephosphorescent polymer compound of the present invention is stable and exhibits ultra-high efficiency in phosphorescent-light emission.
  • the value of m/ (m+n) falls within the range of 0.0001 to 0.5, preferably 0.001 to 0.1. If the value exceeds the range, in other words, the ratio of phosphorescent unit is higher, the light emission efficiency decreases due to aphenomenon called concentration quenching.
  • the phosphorescent units are introduced in the polymer chains at random, however, in some cases, it is preferable that the units are introduced at uniform intervals or in blocks.
  • the phosphorescent unit to be introduced in the copolymer of the present invention may be introduced as the main chain or side chain .
  • the phosphorescent unit it is preferable that the phosphorescent unit has a structure represented by formula (2) below.
  • A represents a phosphorescent organic group
  • X 3 represents the same as X 1 and X 2 defined in formula (1) , that is, a hydrogen atom, a halogen atom, an alkyl group, alkoxy group, an amino group, a cyano group, a carboxyl group, a carbonyl group, a hydroxyl group, an aryl group, an aryloxy group, or a hetero aryl group.
  • the phosphorescent unit is a onovalent, divalent or trivalent group of transitionmetal or rare-earthmetal complex .
  • the phosphorescent unit include metal complexes having an organic ligand represented by formulae (4-1) to (4-5) below, however, are not limited thereto in the present invention.
  • Examples of the ligand used in the transition metal or rare-earth metal complex include acetylacetonate, 2,2' -bipyridine, 4,4' -dimetyl-2, 2' -bipyridine,
  • One or more kinds of such ligands are contained in one complex.
  • the complex compound binuclear complex, multinuclear complex, or composite consisting of two or more of these complexes may be used.
  • transition metal used for the transition metal complex above examples includemetals fromSc (atomicnumber 21) to Zn (atomic number 30) in the first transition element series, Y (atomicnumber 39) toCd (atomicnumber 48) in the secondtransition element series, and Hf (atomic number 72) to Hg (atomic number 80) in the third transition element series.
  • rare-earth metal used for the rare-earth metal complex above examples includemetals fromLa (atomicnumber 57) toLu (atomic number 71) .
  • the substituent in the polysilane unit is selected according to the electron geometry of the phosphorescent unit.
  • PBPS red light is emitted
  • PDBS blue light is emitted
  • main structure indicates the portion "( ) n" in formula (1).
  • the polymerization degree of the copolymer (polymer compound) of the present invention is preferably within the range of from 5 to 5000. If the degree is lower than 5, a film formed using the copolymer can hardly be uniform and crystallization is readily caused, thereby deteriorating stability of the film. Polymer having a polymerization degree exceeding 5000 is difficult to be prepared, and such a polymer does not have good solubility in solvent. Accordingly, polymer having a polymerization degree of 5 to 5000 is used for forming a uniform and stable film.
  • copolymer (phosphorescent polymer compound) of the present invention By using the copolymer (phosphorescent polymer compound) of the present invention, soluble inorganic solvent, athinuniform film can be formed on a substrate by coating method. Further, pattern forming in three primary colors is possible by printing method or ink jet method.
  • the polymer compound of the present invention can be synthesized by various known methods.
  • the following phosphorescent unit precursor is synthesized first. That is, one or more functional groups such as an alkyl group, a hydroxyl group, a carbonyl group, an amino group, an isocyanate group and halogens are introduced to one of the ligands of a transition metal complex having phosphorescence-emitting property. These functional groups may be directly introduced to the transition metal complex . Also, a desired transition metal complex having functional groups in a ligand may be prepared by complex synthesis method such as ligand substitution or the method through binuclear complex after synthesizing a compound having these functional groups introduced to a ligand thereof.
  • one or more functional groups such as an alkyl group, a hydroxyl group, a carbonyl group, an amino group, an isocyanate group and halogens are introduced to one of the ligands of a transition metal complex having phosphorescence-emitting property. These functional groups may be directly introduced to the transition metal complex .
  • a compound such as dichlorosilane and trichlorosilane which is to be a functional group introduced to a polysilane unit, is bonded, so that the ligand of the transition metal is connected to dichlorosilane by an appropriate bonding group having an appropriate length such as alkyl bond, ether bond, ester bond, amide bond and urethane bond.
  • dichlorosilane derivative or trichlorosilane derivative to be a precursor of phosphorescent unit is synthesized.
  • the phosphorescent unit is further reacted with one or more appropriate dichlorosilanes such as dichlorodimethylsilane and dichloromethylphenylsilane, in an appropriate solvent such as benzene, toluene and xylene in the presence of an appropriate metal such as sodium, to thereby prepare the copolymer (polymer) of the invention .
  • an appropriate solvent such as benzene, toluene and xylene
  • an appropriate metal such as sodium
  • this reaction by changing reaction conditions such as concentration and ratio of the precursor of the phosphorescent unit and dichlorosilane, the kind of the solvent, the amount of the metal, reaction time, reaction temperature and the like, a variety of polymers which vary in the concentration ratio of the phosphorescent unit, molecular weight of the polymer andmolecular weight distribution are obtainable. That is, the ratio of the phosphorescent unit to total polymer unit can be adjusted to the range of 0.0001 to 0.5, and also, the polymer
  • a phosphorescent unit is incorporated in the main chain of the polymer chain
  • first the followingprecursor of aphosphorescent unit is synthesized. That is, functional groups selected from an alkyl group, a hydroxyl group, a carbonyl group, an amino group, an isocyanate group, halogen and the like are introduced to the plural ligands of a transition metal complex having phosphorescence-emitting property.
  • the functional groups may be introduced directly to the transition metal complex.
  • a desired transition metal complex having functional groups introduced to ligands may be prepared by ligand substitution or by complex synthesis method through binuclear complex after synthesizing a compound having these functional groups introduced to ligands thereof.
  • an appropriate bonding group having an appropriate length such as alkyl bond, ether bond, ester bond, amidebondandurethanebond.
  • the precursor phosphorescent unit is further reacted with one or more appropriate dichlorosilanes such as dichlorodimethylsilane and dichloromethylphenylsilane, in an appropriate solvent such as benzene, toluene and xylene in the presence of an appropriate metal such as sodium, to thereby prepare the copolymer (polymer) of the invention.
  • dichlorosilanes such as dichlorodimethylsilane and dichloromethylphenylsilane
  • an appropriate solvent such as benzene, toluene and xylene
  • an appropriate metal such as sodium
  • the ratio of the phosphorescent unit to the total polymer unit can be adjusted to the range of 0.0001 to 0.5, and also, the polymerization degree can be adjusted to the range of 5 to 5000.
  • Another method for incorporating a phosphorescent unit into a polymer is that ligand portion of a transition metal complex is synthesized in advance, and then after reacting with an appropriate dichlorosilanes in the same manner as above, the transition metal is complexed on the ligand portion to thereby obtain a desired polymer.
  • dehydrogenationcondensation method Coord. Chem. Rev., Vol.206-207, p.493 (2000)
  • anion polymerization method Mocromolecules, Vol.27, No.8 p.2360 (1994)
  • electro-chemical polymerization method and the like J.Macromol. Sci., Rev. Macromol . Chem. Phys., Vol.c38, No.4 p.637 (1998)).
  • appropriate polymer units can be prepared, and by the combination use of the units, desired polymer compound can be obtained.
  • polymer compound may be used as is, however, may be once or plural times subj ected to purification process such as reprecipitation and column chromatography, which is to be selected according to properties of the polymer compound, to enhance the purity.
  • light-emitting material comprising the copolymer (phosphorescent polymer compound) of the present invention is described below.
  • copolymer (polymer compound) of the present invention itself can be used as light emittingmaterial for organic EL device .
  • the copolymer of the present invention may be mixed with other electron transporting compounds to be used as light emitting material.
  • electron transporting compound to be mixed with the copolymer (polymer compound) of the present invention maybe either low-molecular compound or high-molecular compound.
  • low-molecular compound to be mixed with the polymer compound of the present invention include oxadiazole derivative, triazole derivative, imidazole derivative, triazine derivative and organic metal complex compound, but are not limited to those compounds.
  • high-molecular compound to be mixed with the polymer compound of the present invention compounds polymerized by introducing polymerizable functional group into the above mentioned low-molecular electron-transporting compounds, for instance, polyPBD(PPBD) as disclosed in JP-A-10-1665, can be used, but are not limited to the compound.
  • polymer compound for the purpose of improving properties of a film formed from the copolymer (polymer compound) of the present invention, other polymer compounds, which do not participate in light-emitting property, may be mixed with the polymer compound of the present invention to be used as light emitting material.
  • examples of such a polymer compound include polymerthylmethacrylate (PMMA) which may be added for the purpose of imparting flexibility to the obtained film, but are not limited thereto .
  • the configuration of the organic EL device using the light emitting material comprising the polymer compound of the present invention as a light-emitting layer may include, between an anode and a cathode, a structure selected from (1) hole transporting layer/light emitting layer/electron transporting layer, (2) hole transporting layer/light emitting layer, (3) light emitting layer/electron transporting layer and (4) light emitting layer only.
  • a laminate structure consisting of light emitting layer and electron transporting layer and/or hole transporting layer is preferable.
  • hole transporting material for constituting the hole transporting layer aromatic tertiary a ine derivatives such as triphenylamine and oligomers or polymer thereof, or known hole transporting materials such as N-vinylcarbazole may be used. Polyparaphenylenevinylene or polydialkylfluorene can also be used.
  • electron transporting material for constituting the electron transporting layer knownmaterials such as oxadiazole derivatives, triazole derivatives imidazole derivatives, triazine derivatives and organic metal complex compound as heretofore mentioned may be used.
  • a hole injection layer may be placed between anode and hole transporting layer or light emitting layer.
  • hole injection material for constituting the hole injection layer conductive polymers such as polythiophene derivatives, polypyrrole derivatives and olyaniline derivatives can be used.
  • PEDOT polyethylenedioxythiophene
  • PPS polystyrenesulfonic acid
  • anode which is generally formed on a glass substrate, a light-transmitting material is used.
  • a thin film consisting of metal such as gold, platinumandmagnesiumsilvermaybe used.
  • Conductive polymers consisting of polyaniline, polthiophene or polypyrrole, and derivatives thereof may also be used.
  • alkali metals such as lithium and sodium andalkali earth metals such as magnesium and calcium which have low work function are preferable from the viewpoint of electron injection property.
  • use of stable aluminum is also preferable.
  • the layer may contain two or more materials, and such materials are disclosed in JP-A-2-15595 and JP-A-5-121172.
  • Athin film (of about 0.01 to lOOnm) of alkali metals or alkali earth metals such as cesium, balium, calcium and strontium, or alkali metal compound such as LiF and Li2 ⁇ or alkali earth metal compound such as CaF 2 andSrF 2 maybe insertedbetween aluminumandorganic layer adjacent to the cathode.
  • Anode and cathode can be formed by a conventional method such as vacuum deposition method, sputtering method, ion plating method. Patterning of electrode (especially, transparent electrode) is preferably carried out by chemical etching using photolithography or physical etching using laser and the like, or may be carried out with stacking masks via vacuum deposition or via sputtering.
  • plastic substrate of plastic or metal film may be used as transparent substrate for organic EL device in the present invention.
  • metal film organic or inorganic insulating layer is coated on the film before the metal film is used as substrate.
  • Plastic material used for substrate requires excellent heat-resistance, dimensional stability, solvent-resistance, insulation property, processability, low-air-permeability andnonhygroscopicproperty. Use of flexible material leads to provision of flexible organic EL device.
  • moisture-impermeable layer On one or both of the surface facing the electrode and the opposite surface of the substrate, moisture-impermeable layer (gas barrier layer) is preferably placed.
  • material for the moisture-impermeable layer inorganic materials such as silicon nitride and silicon oxide are preferably employed, and the layer can be formed by radio frequency sputtering method or the like.
  • Two or more transistors per organic EL (organic luminescent) pixel formed on the substrate are placed, and by addressing and driving through the transistors, active-type display device can be provided.
  • An organic transistor comprising an organic compound as its active layer enables application to a plastic substrate.
  • Example 1-1 Synthesis of dichloromethylphenylsilane derivative [ (2-(3-( (4-dichloromethylsilylphenyl)methyloxy) phenyl) pyridine)bis (2-phenylpyridine) iridium (III) ]
  • dichloromethylphenylsilane derivative (2-(3-( (4-dichloromethylsilylphenyl)methyloxy) phenyl) pyridine)bis (2-phenylpyridine) iridium (III)
  • 3-MeO-PPy 2- (3-methoxyphenyl) pyridine
  • (3-methoxyphenyl) magnesium bromide was synthesized from 22.4 g (120 mmol) of 3-bromoanisole with 3.4 g of magnesium (Mg) in dry tetrahydrofuran (THF) in an argon streamby a conventional manner . This was slowly added to a dry THF solution of 15.8 g (100 mmol) of 2-bromopyridine and 1.8 g of (1, 2-bis (diphenylphosphino) -ethane) dichloronickel (II) (Ni (dppe) Cl 2 ) and the mixture was stirred at 50°C for 1 hour .
  • TDMS-C1 tert-butyldimethylsilyl chloride
  • [Ir (PPy) 2 C1] 2 synthesized by a conventional method in the presence of silver (I) trifluoromethanesulfonate (AgCF 3 S0 3 ) . That is, as shown in the Reaction Scheme (4) below, 2.70 g of AgCF 3 S0 3 was added to a suspension of 5.71 g (20.0mmol) of 3-SiO-PPy and 5.37 g (5.0mmol) of [Ir (PPy) 2 C1] 2 in dry toluene and refluxed for 6 hours.
  • AgCF 3 S0 3 silver trifluoromethanesulfonate
  • the silyl group of Ir (PPy) 2 (3-SiO-PPy) was hydrolyzed by a conventional method. That is, as shown in the Reaction Scheme (5) below, 5.1 ml of a 1 M THF solution of tetra-n-butylammonium fluoride (TBAF) was added to a THF solution of 2.00 g (2.55 mmol) of Ir (PPy) 2 (3-SiO-PPy) and the mixture was allowed to react at room temperature for 30 minutes.
  • TBAF tetra-n-butylammonium fluoride
  • Example 1-2 Polymerization of Ir (PPy) 2 (4-DCMPS-3-MeO-PPy) /dichloromethylphenylsilane (DCMPS) copolymer
  • Copolymer of Ir (PPy) 2 (4-DCMPS-3-MeO-PPy) and DCMPS was polymerized by a conventional method. That is, as shown in the Reaction Scheme (8) below, a mixture of 230mg (l ⁇ mmol)of sodium and 20ml of toluene was heated to reflux and well stirred. Thereto dropped was 10 ml of a toluene solution having 35mg (0.04mmol) of Ir(PPy) 2 (4-DCMPS-3-MeO-PPy) and 765mg (4mmol) of DCMPS dissolved therein.
  • the phosphorescent polysilane obtained in Example 1-2 was dissolved in dichloroethane to prepare a 1 mass% solution.
  • a light emitting layer having a thickness of lOOnm by a spin coating method at a spin speed of 1,000 rpm. This was sufficiently vacuum-dried, and 30 nm calcium and lOOnm aluminum were formed by vacuum deposition method.
  • the device was sealed in a glove box filled with high-puritynitrogengas.
  • Ir (PPy) 2 [1- (OH-Bu) -acac] (9-hydroxy-2, 4-nonandionate) bis (2-phenylpyridine) iridium. That is, as shown in the Reaction Scheme (10) below, to a solution of 167 mg (0.26 mmol) of Ir (PPy) 2 (1-Bu-acac) in 10 ml of THF was dripped 1.0 ml (0.5 mmol) of a 0.5 M THF solution of 9-borabicyclo [3.3.1] nonane (hereinafter abbreviated as 9-BBN) and the solution was heated to reflux for 25 minutes.
  • 9-BBN 9-borabicyclo [3.3.1] nonane
  • Ir (PPy) 2 [4-BrP-Meo-acac] (2-phenylpyridine) iridium
  • Example 2-2 Polymerization of Ir (PPy) 2 [4-DCMPS-MeO-acac] / dichloromethylphenylsilane (DCMPS) copolymer
  • copolymer of Ir (PPy) 2 [4-DCMPS-MeO-acac] and DCMPS was polymerized. That is, a mixture of 23Omg (lOmmol) of sodium and 20ml of toluene was heated to reflux and well stirred. Thereto dropped was 10 ml of a toluene solution having 32mg (0.04mmol) of Ir (PPy) 2 [4-DCMPS-MeO-acac] and 765mg (4mmol) of DCMPS dissolved therein.
  • Example 2-3 For the purpose of enhancing electron transporting property of light emitting layer and facilitating hole injection into light-emitting layer, a conductive polymer layer was inserted and electron transporting compound was mixed into the light emitting layer.
  • conductive polymer layer of PEDT/PPS was formed to a thickness of 50nm by a spin coating method and dried at about 180°C.
  • Example 3-1 Synthesis of dichloromethylsilane derivative [ (5- (4-dichloromethylsilylphenyl)methyloxymethyl) -picolinato] bis (2- (2, 4-difluorophenyl) pyridine) iridium (III)
  • 2- (2, 4-difluorophenyl) pyridine (hereinafter abbreviated as "2,4-F-PPy") was synthesized by a conventional method. That is, under argon stream, 8.69 g (55.0 mmol) of 2-bromopyridine was dissolved in 200 ml of dry tetrahydrofuran and cooled to -78°C.
  • N,N-dimethylformamide (DMF) was added to a mixture of 121.6 mg
  • Ir (2, 4-F-PPy) 2 ( 4-BrP-MeO-pic)
  • Ir (2, 4-F-PPy) 2 ( 4-BrP-MeO-pic)
  • O.llg (0.15mmol) of Ir (2, 4-F-PPy) 2 (5-HO-pic) was dissolved in a 10 ml DMSO solution having 28 mg (0.5 mmol) of KOH dissolved therein, and further to this solution was added 50mg (0.2mmol) of BBB, followed by stirring for 8 hours at room temperature. Then, 200 ml of dilute hydrochloric acid solution and 50 ml of chloroform were added to the reaction mixture and the obtained mixture was stirred vigorously.
  • the chloroform layer was separated and dried over magnesium sulfate and the solvent was distilledoffunder reducedpressure .
  • the obtainedyellowresidue was dissolved in dichloromethane and the solution was subjected to silica gel column chromatography with the dichloromethane as eluent to separate a pale yellow main product. Solution of this product was concentrated under reduced pressure and then a small amount of hexane was added thereto, followed by cooling to -20°C to obtain 44.8 mg (0.05 mmol) of the objective Ir (2, 4-F-PPy) 2 (4-BrP-MeO-pic) as pale yellow crystal. Identification was performed by 1 H-NMR and CHN elementary analysis .
  • Ir (2, 4-F-PPy) 2 (4-DCMPS-MeO-Pic) was synthesized. That is, as shown in the Reaction Scheme (18) below, amixture of 3.6g (0.15mmol) ofmagnesium and50 ml of diethyl ether was stirred well, and thereto added dropwise was 15ml of a diethyl ether solution having 114mg (0.135mmol) of Ir (2, 4-F-PPy) 2 (4-BrP-MeO-pic) dissolved therein, followed by stirring for 12 hours .
  • Example 3-2 Polymerization of copolymer of Ir (2, 4-F-PPy) 2 (4-DCMPS-MeO-pic) /DCMPS
  • Copolymer of Ir (2, 4-F-PPy) 2 (4-DCMPS-MeO-pic) and DCMPS was polymerized. That is, as shown in Reaction Scheme (19) below, a mixture of 230mg (lOmmol) of sodium and 20ml of toluene was heated to reflux and well stirred. Thereto dropped was 10 ml of a toluene solution having 35mg (0.04mmol) of Ir (2,4-F-PPy) 2 (4-DCMPS-MeO-pic) and 765mg (4mmol) of DCMPS dissolved therein.
  • conductive polymer layer PEDT/PPS was formed on a washed ITO-coated glass substrate. Thereon spin coated was a dichloroethane solution (lmass%) having mixed therein 70 mass% of the phosphrescent polysilane obtained in Example 3-2 and 30 mass% of oxadiazole derivative OXD-7 (product name, manufactured by Nihon SiberHegner K.K.) represented by formula (8) below. After sufficient drying, electrode Ca (lOnm) /Al (150nm) was formed. Thus obtained device was sealed and properties were measured. Blue light emitted from a phosphorescent unit was observed, and the value of the external quantum efficiency was 5%.
  • the phosphorescent polymer compound of the present invention with chemical structural units having phosphorescent property being introduced in the polymer chains of silicone-base polymer, is stable and exhibits ultra-high efficiency in phosphorescence emission, especially blue phosphorescence emission.
  • the organic EL device of the present invention which is fabricated by wet-coating method using solution, realizes large-area display panel, high luminous efficiency and longer operating life, and therefore preferably applicable to information display panel having a larger-area, lighting apparatus and the like.

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Abstract

L'invention concerne un composé polymère phosphorescent permettant l'émission permanente de phosphorescence bleue à efficacité quantique particulièrement élevée. Ce composé comporte une unité répétitive phosphorescente et une unité répétitive de formule (1) : (1) dans laquelle X1 et X2 représentent indépendamment un atome hydrogène, un atome halogène, un groupe alkyle, un groupe alcoxy, un groupe amino, un groupe cyano, un groupe carboxyle, un groupe carbonyle, un groupe hydroxyle, un groupe aryle, un groupe aryloxy ou un groupe hétéroaryle. La présente invention porte également sur une matière émettant de la lumière et sur un dispositif organique électroluminescent (EL) doté dudit composé
PCT/JP2003/005352 2002-04-26 2003-04-25 Compose polymere phosphorescent, matiere emettant de la lumiere et dispositif organique electroluminescent (el) dote de ce compose WO2003092334A1 (fr)

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WO2005124889A1 (fr) * 2004-06-09 2005-12-29 E.I. Dupont De Nemours And Company Composés organométalliques et dispositifs faits de ces composés
WO2007039383A1 (fr) * 2005-10-04 2007-04-12 Wacker Chemie Ag Melanges phosphorescents
WO2010062643A1 (fr) * 2008-10-28 2010-06-03 The Regents Of The University Of Michigan Oled blanche empilée présentant des sous-éléments rouges, verts et bleus séparés
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GB2421242A (en) * 2003-08-04 2006-06-21 Sumitomo Chemical Co Aromatic monomer-and conjugated polymer-metal complexes
WO2005016945A1 (fr) * 2003-08-04 2005-02-24 Sumitomo Chemical Company, Limited Complexes metalliques a base de monomere aromatique et de polymere conjugue
GB2421242B (en) * 2003-08-04 2008-01-02 Sumitomo Chemical Co Aromatic monomer-and conjugated polymer-metal complexes
CN1950480B (zh) * 2004-05-11 2011-09-28 默克专利有限公司 新型电致发光材料混合物
KR101206315B1 (ko) 2004-05-11 2012-11-29 메르크 파텐트 게엠베하 전계발광 중합체
WO2005111113A1 (fr) 2004-05-11 2005-11-24 Merck Patent Gmbh Polymeres electroluminescents
WO2005111172A3 (fr) * 2004-05-11 2006-01-05 Covion Organic Semiconductors Nouveaux melanges de materiaux pour applications electroluminescentes
WO2005111172A2 (fr) * 2004-05-11 2005-11-24 Merck Patent Gmbh Nouveaux melanges de materiaux pour applications electroluminescentes
US8058790B2 (en) 2004-05-11 2011-11-15 Merck Patent Gmbh Material mixtures for use in electroluminescence
KR101206316B1 (ko) * 2004-05-11 2012-11-29 메르크 파텐트 게엠베하 전자발광용 신규한 재료 혼합물
WO2005124889A1 (fr) * 2004-06-09 2005-12-29 E.I. Dupont De Nemours And Company Composés organométalliques et dispositifs faits de ces composés
US9000166B2 (en) 2005-07-08 2015-04-07 Merck Patent Gmbh Metal complexes
WO2007039383A1 (fr) * 2005-10-04 2007-04-12 Wacker Chemie Ag Melanges phosphorescents
WO2010062643A1 (fr) * 2008-10-28 2010-06-03 The Regents Of The University Of Michigan Oled blanche empilée présentant des sous-éléments rouges, verts et bleus séparés
US8766291B2 (en) 2008-10-28 2014-07-01 The Regents Of The University Of Michigan Stacked white OLED having separate red, green and blue sub-elements
CN102197507A (zh) * 2008-10-28 2011-09-21 密执安州立大学董事会 具有单独的红色、绿色和蓝色子元件的堆叠式白色oled
US9065067B2 (en) 2008-10-28 2015-06-23 The Regents Of The University Of Michigan Stacked white OLED having separate red, green and blue sub-elements
CN110551285A (zh) * 2018-06-01 2019-12-10 中国科学院大连化学物理研究所 一种铱催化脱氢偶联合成聚硅醚
CN115161014A (zh) * 2022-06-09 2022-10-11 昆明理工大学 一种掺杂型室温磷光水性聚合物防伪材料的制备方法及其应用
CN115161014B (zh) * 2022-06-09 2023-04-07 昆明理工大学 一种掺杂型室温磷光水性聚合物防伪材料的制备方法及其应用

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