WO2005061655A1 - Utilisation de chelates de gadolinium(iii) servant de matieres luminescentes dans des diodes organiques electroluminescentes (oled) - Google Patents

Utilisation de chelates de gadolinium(iii) servant de matieres luminescentes dans des diodes organiques electroluminescentes (oled) Download PDF

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WO2005061655A1
WO2005061655A1 PCT/EP2004/014494 EP2004014494W WO2005061655A1 WO 2005061655 A1 WO2005061655 A1 WO 2005061655A1 EP 2004014494 W EP2004014494 W EP 2004014494W WO 2005061655 A1 WO2005061655 A1 WO 2005061655A1
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iii
gadolinium
complexes
light
emitting layer
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English (en)
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Arnd Vogler
Andreas Strasser
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Basf Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/77—Preparation of chelates of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • 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
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • 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
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • 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

  • Gadolinium (III) chelates as luminescent materials in organic light-emitting diodes (OLEDs)
  • the present invention relates to the use of gadolinium (III) complexes as emitter molecules in organic light-emitting diodes (OLEDs), the use of the gadolinium (III) complexes as light-emitting layer in OLEDs, a light-emitting layer containing at least one gadolinium (III). Complex, an OLED containing this light-emitting layer and devices that contain an OLED according to the invention.
  • OLEDs organic light-emitting diodes
  • OLEDs organic light-emitting diodes
  • the property of materials is used to emit light when they are excited by electrical current.
  • OLEDs are particularly interesting as an alternative to cathode ray tubes and liquid crystal displays for the production of flat screens. Due to the very compact design and the intrinsically lower power consumption, devices containing OLEDs are particularly suitable for mobile applications, for example for applications in cell phones, laptops, etc.
  • JP 01-256584 relates to an electroluminescent thin film element which contains a rare earth metal complex as a luminescent material.
  • Complexes of the following formulas are mentioned as suitable complexes
  • EP-A 0 556 005 relates to compounds which are obtained by reacting an imido reagent such as diphenylphosphonimido-triphenylphosphorane with a chelate of a transition metal, a lanthanide or an actinide, for example tris (dibenzoylmethide) europium (III).
  • an imido reagent such as diphenylphosphonimido-triphenylphosphorane
  • the compounds fluoresce when irradiated with UV light.
  • Suitable chelates have one or more diketonato ligands.
  • US 5,757,026 relates to a multicolor display containing a plurality of multicolor OLEDs.
  • Each LED contains a light-emitting layer that has an organic material, which can be a metal-acetylacetonate complex. These are preferably used to generate an emission in the blue region of visible light and preferably contain Al 3+ , Ga 3+ and In 3+ as metals. Concrete metal acetylacetonate complexes are not mentioned in US 5,757,026.
  • JP 11-260552 relates to organic light-emitting diodes which contain rare earth metal acetylacetonate complexes as light-emitting material and which have two perfluoroalkyl, perfluoroalkenyl, perfluoroaryl or perfluoroaralkyl groups.
  • Examples are Eu complexes of the formulas Eu (CF 3 COCHCOCF 3 ) 3 , Eu (C 2 F 5 COCHCOC 2 F 5 ) 3 , Eu (C 6 F 5 COCHCOC 6 F 5 ) 3 and Eu (CF 3 COCHCOC 6 F5 ) Called 3 .
  • US Pat. No. 6,524,727 relates to electroluminescent materials and organic light-emitting diodes which contain rare earth, actinide or transition metal complexes which have a diphenylphosphonimide-trisphenylphosphine ligand.
  • the complexes preferably contain diketonato groups as chelating groups.
  • Preferred metals are Sm (III), Eu (III), Tb (III), Dy (III), Yb (III), Lu (III), Gd (III), Eu (II), U (III), UO 2 (IV) and Th (III). Specific examples are disclosed for Tb (III), Eu (III), Dy (III) and UO 2 (IV).
  • Electroluminescence is understood to mean both electrofluorescence and electrophosphorescence.
  • the object of the present application is therefore to provide compounds which are suitable for electroluminescence in the blue, red and green regions of the electromagnetic spectrum, which enables the production of full-color displays. Furthermore, it is an object of the present application to provide compounds which can be used in substance, without host substances, as a light-emitting layer in OLEDs.
  • This task is accomplished by using
  • Gadolinium (III) complexes selected from the group consisting of Gadolinium (III) diketonato complexes of the formula (I)
  • R 3 , R 4 , R 5 independently of one another are a substituted or unsubstituted aryl, alkyl, heteroaryl or alkenyl group
  • R 1 and R 3 are preferably, independently of one another, C to C 4 alkyl, phenyl, pyridyl, imidazolyl, furyl , Thienyl, CF 3 , C 2 F 5 . or C 6 F 5 ; preferably methyl, ethyl, thienyl or CF 3 , particularly preferably thienyl or CF 3
  • R 4 and R 5 are independently C to C 4 alkyl, phenyl, 1-naphthyl, 2-naphthyl;
  • R 2 H a substituted or unsubstituted aryl, alkyl, heteroaryl or alkenyl group, preferably H, C to C 4 alkyl, CF 3 , phenyl; neutral ' ligand, preferably selected from the group consisting of water, ' pyridine, preferably 4-NN-
  • gadolinium (III) complexes of the formulas I and II according to the present application are suitable as light-emitting substances in OLEDs for the production of full-color displays.
  • Gadolinium (III) complexes of the formulas I and II are preferably used, in which the
  • R 1 , R 3 independently of one another are C to C 4 alkyl, phenyl, pyridyl, imidazolyl, furyl, thienyl, CF 3 , C 2 F 5 or C 6 F 5 ; preferably methyl, ethyl, thienyl or CF 3 , particularly preferably thienyl or CF 3 ;
  • R 4 , R 5 independently of one another are C to C 4 -alkyl, phenyl, 1-naphthyl, 2-naphthyl;
  • R 2 H C r to C 4 alkyl, CF 3 , phenyl; n, m 0 or 1, preferably 0.
  • aryl radical or group, heteroaryl radical or group, alkyl radical or group, alkenyl radical or group, arylene radical or group and heteroarylene radical or group have the following meanings:
  • An aryl radical is to be understood as a radical with a backbone of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is composed of an aromatic ring or several fused aromatic rings. Suitable basic structures are, for example, phenyl, naphthyl, anthracenyl or phenanthrenyl.
  • This backbone can be unsubstituted (ie that all carbon atoms that can be substituted carry hydrogen atoms) or can be substituted at one, more or all substitutable positions of the backbone.
  • Suitable substituents are, for example, alkyl residues, preferably alkyl residues with 1 to 8 carbon atoms, particularly preferably methyl, ethyl, i-propyl or t-butyl, aryl residues, preferably C 6 aryl residues, which in turn can be substituted or unsubstituted, heteroaryl residues, preferably heteroaryl residues, which contain at least one nitrogen atom, particularly preferably pyridyl radicals, alkenyl radicals, preferably alkenyl radicals which carry a double bond, particularly preferably alkenyl radicals with a double bond and 1 to 8 carbon atoms, or groups with donor or acceptor action.
  • Groups with a donor effect are to be understood as groups which have a + 1 and / or + M effect and groups with an acceptor effect To understand groups that have an -I and / or -M effect.
  • Suitable groups with donor or acceptor action are halogen residues, preferably F, Cl, Br, particularly preferably F. alkoxy residues, carbonyl residues, ester residues, amine residues, amide residues, CH 2 F groups, CHF 2 groups, CF 3 groups, CN groups Groups, thio groups or SCN groups.
  • the aryl radicals very particularly preferably carry substituents selected from the group consisting of methyl, F, Cl and alkoxy, or the aryl radicals are unsubstituted.
  • the aryl radical or the aryl group is preferably a C 6 aryl radical or a naphthyl radical which is optionally substituted by at least one of the abovementioned substituents.
  • the C 6 aryl radical particularly preferably has none, one or two of the abovementioned substituents, the one substituent preferably being arranged in the para position to the further linking point of the aryl radical and - in the case of two substituents - each in the meta position further linkage point of the aryl radical are arranged or all H atoms of the C 6 aryl radical are substituted by F, that is to say C 6 F 5 .
  • the C 6 aryl radical is very particularly preferably an unsubstituted phenyl radical or C 6 F 5 .
  • the naphthyl radical is preferably 1-naphthyl or 2-naphthyl.
  • a heteroaryl radical or a heteroaryl group is understood to mean radicals which differ from the aryl radicals mentioned above in that at least one carbon atom in the basic structure of the aryl radicals is replaced by a hetero atom.
  • Preferred heteroatoms are N, O and S.
  • the basic structure is particularly preferably selected from systems such as pyridyl, imidazolyl, cyclic esters, cyclic amides and five-membered heteroaromatics such as thienyl, pyrryl, furyl.
  • the basic structure can be substituted at one, more or all substitutable positions of the basic structure. Suitable substituents are the same as those already mentioned for the aryl groups. Thienyl is particularly preferred.
  • An alkyl radical or an alkyl group is a radical with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, very particularly preferably 1 to 4 carbon atoms.
  • This alkyl radical can be branched or unbranched and optionally interrupted by one or more heteroatoms, preferably N, O or S.
  • the alkyl radical or the alkyl group can be a C 3 to C 8 cycloalkyl radical, preferably a C 5 or C 6 cycloalkyl radical, which can optionally be interrupted by one or more heteroatoms, preferably N, O or S, for example cyclopentyl and cyclohexyl.
  • this alkyl radical can be substituted with one or more of the substituents mentioned in relation to the aryl groups, in particular halogen radicals, preferably F, Cl, Br, particularly preferably F. It is also possible for the alkyl radical to carry one or more aryl groups. Are all of the aryl groups listed above are suitable.
  • the alkyl radicals are particularly preferably selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl; n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neo-pentyl, n-hexyl, i-hexyl, sec-hexyl, cyclopentyl, cyclohexyl, CF 3 and C 2 F 5 .
  • Methyl, ethyl, i-propyl, n-hexyl, CF 3 and C 2 F 5 are very particularly preferred.
  • alkenyl radical or an alkenyl group is understood to mean a radical which corresponds to the above-mentioned alkyl radicals having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl radical is replaced by a C-C double bond.
  • the alkenyl radical preferably has one or two double bonds.
  • Preferred gadolinium (IH) complexes of the formula I are those in which R 1 and R 3 independently of one another are C to C 4 -alkyl, phenyl, pyridyl, imidazolyl, furyl, thienyl, CF 3 , C 2 F 5 or C 6 F 5 , particularly preferably methyl, ethyl, thienyl or CF 3 , very particularly preferably thienyl or CF 3 and R 2 , H, C r C 4 alkyl, phenyl, preferably H means, p preferably means in the gadolinium (III) - Complexes of the formula I 0 or 1, particularly preferably 0.
  • p in the gadolinium (H]) complexes of the formula II preferably denotes 0 or 1, particularly preferably 0.
  • transition metal complexes mentioned above are outstandingly suitable as emitter molecules in organic light-emitting diodes (OLEDs). Simple variations of the ligands make it possible to provide transition metal complexes which show electroluminescence in the red, green and in particular in the blue region of the electromagnetic spectrum.
  • the neutral transition metal complexes used according to the invention are therefore suitable for use in technically usable full-color displays.
  • GadoIinium (III) complexes are prepared by methods known to those skilled in the art. -
  • Typical methods are, for example, deprotonation of the ligand precursors corresponding to the ligands of the compounds of the formulas I and II and subsequent, generally in situ, reaction with suitable metal complexes containing Gd. Furthermore, the preparation of the gadolinium (III) complexes of the formulas I and II is possible by direct reaction of the neutral ligand precursors corresponding to the ligands of the gadolinium (III) complexes with the suitable gadolinium (III) complexes, which is preferred.
  • Suitable ligand precursors which lead to the ligands of the godinium (III) complexes of the formulas I and II are known to the person skilled in the art.
  • ligands are deprotonated, this can be done by basic metal salts, basic anions such as acetates, acetylacetonates, carbonates or alkoxylates or external bases such as KO'Bu, NaO'Bu, LiO l Bu, NaH, silylamides and phosphazene bases.
  • gadolinium complexes which can be used as the starting compound are known to the person skilled in the art. GdCl 3 x 2H 2 0 is particularly preferably used.
  • the reaction is preferably carried out in a solvent.
  • Suitable solvents are known to the person skilled in the art and are preferably selected from water and alcohols such as ethanol and mixtures thereof.
  • the molar ratio of gadolinium complex used to ligand precursor used is preferably 0.7: 3.0 to 1.5: 3.0, particularly preferably 0.9: 3.0 to 1.1, very particularly preferably 1: 3.
  • the gadolinium (III) complexes of the formulas I and II are preferably obtained by directly reacting the corresponding ligand precursor with a gadolinium complex. This reaction is particularly preferably carried out in water or an alcohol or mixtures thereof in the molar ratios of gadolinium complexes and ligand precursors already mentioned above.
  • the reaction is generally carried out at temperatures from 0 to the reflux temperature of the solvent, preferably 10 to 50 ° C., particularly preferably at room temperature.
  • the reaction time depends on the desired gadolinium (III) complex and is generally from 10 minutes to 50 hours, preferably from 20 minutes to 24 hours, particularly preferably from 0.5 hours to 12 hours.
  • the gadolinium complex of the formulas I and II obtained is worked up by methods known to the person skilled in the art.
  • the product is precipitated by adding water and the precipitated product is filtered, washed, for example with water, and then dried.
  • the gadolinium (III) complexes of the formulas I or II used according to the invention are outstandingly suitable as emitter substances, since they have luminescence (electroluminescence) in the visible range of the electromagnetic spectrum.
  • the gadolinium (III) complexes used as emitter substances according to the invention it is possible to provide compounds which have electroluminescence in the red, green and blue regions of the electromagnetic spectrum. So it is possible with the help of To provide gadolinium (III) complexes used according to the invention as emitter substances for full-color displays which can be used technically.
  • gadolinium (III) complexes of the formulas I and II show luminescence in the solid state, particularly preferably electroluminescence, in the visible range of the electromagnetic spectrum.
  • These complexes which are luminescent in the solid state can be used in bulk, that is to say without any further additives, as emitter substances in OLEDs.
  • an OLED can be produced with a light-emitting layer, with no complex cover evaporation of a matrix material with the emitter substance being necessary.
  • gadolinium (III) complexes of the formulas I and II are also subject of the present application.
  • Organic light-emitting diodes are basically made up of several layers:
  • the gadolinium (III) complexes of the formulas I and II are preferably used in the light-emitting layer as emitter molecules. Another object of the present application is therefore a light-emitting layer containing at least one gadolinium (III) complex of the formulas I and II as an emitter molecule. Preferred gadolinium (III) complexes of the formulas I and II have already been mentioned above.
  • the gadolinium (III) complexes of the formulas I and II used according to the invention can be present in substance - without further additives - in the light-emitting layer.
  • further compounds are present in the light-emitting layer.
  • a fluorescent dye can be present in order to change the emission color of the gadolinium (III) complex used as the emitter molecule.
  • a dilution material can also be used. This dilution material can be a polymer, for example Poly (N-vinyl carbazole) or polysilane.
  • the diluent can also be a small molecule, for example 4,4'-N, N'-dicarbazole biphenyl (CDP) or tertiary aromatic amines.
  • CDP 4,4'-N, N'-dicarbazole biphenyl
  • the proportion of the gadolinium (III) complexes used according to the invention in the light-emitting layer is generally less than 20% by weight, preferably 3 to 10% by weight.
  • the Gadoli ⁇ ium (III) complexes of the formulas I and II are preferably used in substance, as a result of which costly cover evaporation of the Gadolinium (III) complexes with a matrix material (diluent material or fluorescent dye) is avoided.
  • the gadolinium (III) complexes luminesce in the solid.
  • the gadolinium (III) complexes of the formulas I and II show luminescence in the solid state.
  • the light-emitting layer preferably contains at least one gadolinium (III) complex of the formula I or II and no matrix material selected from the dilution material and fluorescent dye.
  • Another object of the present application is, in a preferred embodiment, a light-emitting layer consisting of at least one gadolinium (III) complex of the formulas I and / or II as an emitter molecule.
  • III gadolinium
  • Each of the aforementioned layers of the OLED can be constructed again of 2 or more layers.
  • the hole-transporting layer can be constructed from a layer into which holes are injected from the electrode and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron-transporting layer can also consist of several layers, for example a layer in which electrons are injected through the electrode and a layer which receives electrons from the electron-injecting layer and transports them into the light-emitting layer. These layers are selected according to factors such as energy level, temperature resistance and charge mobility, as well as the energy difference of the layers with the organic layers or the metal electrodes.
  • the person skilled in the art is able to choose the structure of the OLEDs in such a way that it is optimally adapted to the gadolinium (III) complexes used as emitter substances according to the invention.
  • the HOMO (highest occupied molecular orbital) of the hole-transporting layer should match the work function of the anode and the LUMO (lowest unoccupied molecular orbital) electron transporting layer should match the work function of the cathode.
  • Another object of the present application is an OLED containing at least one light-emitting layer according to the invention.
  • the further layers in the OLED can be constructed from any material that is usually used in such layers and is known to the person skilled in the art.
  • the anode (1) is an electrode that provides positive charge carriers.
  • it can be constructed from materials that contain a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides.
  • the anode can be a conductive polymer. Suitable metals include the metals of Groups Ib, IVa, Va and Via of the Periodic Table of the Elements and the transition metals of Group VIII. If the anode is to be translucent, mixed metal oxides of Groups Mb, Illb and IVb of the Periodic Table of the Elements are generally used , for example indium tin oxide (ITO).
  • ITO indium tin oxide
  • the anode (1) contains an organic material, for example polyaniline, as described, for example, in Nature, vol. 357, pages 477 to 479 (June 11, 1992). At least either the anode or the cathode should be at least partially transparent in order to be able to couple out the light formed.
  • organic material for example polyaniline
  • Suitable hole transport materials for the layer (2) of the OLED according to the invention are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technologie, 4th edition, vol. 18, pages 837 to 860, 1996. Both hole transporting molecules and polymers can be used as hole transport material.
  • Holes used to transport holes are selected from the group consisting of 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl ( ⁇ -NPD), N, N'-diphenyl-N, N '-bis (3-methylphenyl) - [, 1' -biphenyl] -4,4'-diamine (TPD), 1, 1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N '-Bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl) - [1, 1' - (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA), ⁇ -phenyl-4-N, N-dip
  • dehyddiphenyIhydrazone ' DEH
  • triphenylamine TPA
  • bis [4- (N, N-diethylamino) -2-methylphenyl) (4-methy) -phenyl) methane MPMP
  • MPMP bis [4- (N, N-diethylamino) -2-methylphenyl) (4-methy) -phenyl) methane
  • MPMP 1-phenyl-3- [p- ( diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP)
  • 1, 2-trans-bis (9H-carbazol-9-yl) cyclobutane DCZB
  • N, N, N ', N'-tetrakis (4-methylphenyl) - (1, 1'-biphenyl) -4,4'-diamine TB
  • porphyrin compounds such as copper
  • hole transporting polymers are selected from the group consisting of polyvinyl carbazoles, (phenylmethyl) polysilanes and polyanilines. It is also possible to obtain hole transporting polymers by doping hole transporting molecules in polymers such as polystyrene and polycarbonate. Suitable molecules which transport holes are the molecules already mentioned above.
  • Suitable electron-transporting materials for the layer (4) of the OLEDs according to the invention include metals chelated with oxinoid compounds such as tris (8-quinolinato) aluminum (AIq 3 ), compounds based on phenanthroline such as 2,9-dimethyl, 4,7-diphenyl-1, 10-phenanthroline (DDPA) or 4,7-diphenyl-1, 10-phenanthroline (DPA) and azole compounds such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) - 1, 3,4-oxadiazole ( PBD) and 3- (4-biphenylyI) -4-phenyl-5- (4-t-butylphenyl) -1, 2,4-triazole
  • oxinoid compounds such as tris (8-quinolinato) aluminum (AIq 3 )
  • DDPA 10-phenanthroline
  • DPA 4,7-diphenyl-1, 10-phenanthroline
  • azole compounds such as 2- (4-b
  • the layer (4) can serve both to facilitate electron transport and as a buffer layer or as a barrier layer in order to avoid quenching of the exciton at the interfaces of the layers of the OLED. ⁇ Preferably, the layer (4) improves the mobility of electrons and reduces quenching of the exciton.
  • the cathode (5) is an electrode that is used to introduce electrons or negative charge carriers.
  • the cathode can be any metal or non-metal that has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1, for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the periodic table of the elements, comprising the rare earth metals and the lanthanides and actinides. Metals such as aluminum, indium, calcium, barium, samarium and magnesium as well as combinations thereof can also be used. Furthermore, lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode in order to reduce the operating voltage.
  • the OLED according to the present invention can additionally contain further layers which are known to the person skilled in the art.
  • a layer can be applied between the layer (2) and the light-emitting layer (3), which facilitates the transport of the positive charge and / or adjusts the band gap of the layers to one another.
  • this additional layer can serve as a protective layer.
  • additional layers can be present between the light-emitting layer (3) and the layer (4) in order to facilitate the transport of the negative charge and / or to match the band gap between the layers.
  • this layer can serve as a protective layer.
  • the OLED according to the invention contains, in addition to the layers (1) to (5), at least one of the further layers mentioned below: a hole injection layer between the anode (1) and the hole-transporting layer (2); - A block layer for electrons between the hole-transporting layer (2) and the light-emitting layer (3); a block layer for holes between the light-emitting layer (3) and the electron-transporting layer (4); an electron injection layer between the electron transporting layer (4) and the cathode (5).
  • suitable materials for example on the basis of electrochemical tests. Suitable materials for the individual layers are known to the person skilled in the art and are disclosed, for example, in WO 00/70655.
  • each of the named layers of the OLED according to the invention can be made up of two or more layers. Furthermore, it is possible that some or all of the layers (1), (2), (3), (4) and (5) are surface-treated in order to increase the efficiency of the charge carrier transport. The choice of materials for each of the layers mentioned is preferably determined by obtaining an OLED with high efficiency.
  • the OLED according to the invention can be produced by methods known to the person skilled in the art. Generally, the OLED is replaced by successive ones
  • Suitable substrates are, for example, glass or polymer films.
  • the organic layers can be made from solutions or dispersions in suitable solvent
  • Solvents are coated, known to those skilled in the art
  • the different layers have the following thicknesses: anode (2) 500 to 5000 ⁇ , preferably 1000 to 2000 ⁇ ; Hole-transporting layer (3) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ , light-emitting layer (4) 10 to 1000 ⁇ , preferably 100 to 800 ⁇ , electron-transporting layer (5) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ 'cathode (6) 200 to 10,000 ⁇ , preferably 300 to 5000 ⁇ .
  • the position of the recombination zone of holes and electrons in the OLED according to the invention and thus the emission spectrum of the OLED can be influenced by the relative thickness of each layer.
  • the thickness of the electron transport layer should preferably be chosen so that the electron / hole recombination zone lies in the light-emitting layer.
  • the ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used. The layer thicknesses of any additional layers used are known to the person skilled in the art.
  • OLEDs By using the gadolinium (III) complexes of the formulas I or II used as emitter molecules in the light-emitting layer of the OLEDs according to the invention, OLEDs can be obtained with high efficiency.
  • the efficiency of the OLEDs according to the invention can also be improved by optimizing the other layers.
  • highly efficient cathodes such as Ca, Ba or LiF can be used.
  • Shaped substrates and new hole-transporting materials which reduce the operating voltage or increase the quantum efficiency can also be used in the OLEDs according to the invention.
  • additional layers can be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
  • the OLEDs according to the invention can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances as well as billboards, lighting and information boards. Mobile screens are e.g. Screens in cell phones, laptops, vehicles and destination displays on buses and trains.
  • gadolinium (III) complexes of the formulas I or II used according to the invention can be used in OLEDs with an inverse structure.
  • the gadolinium (HI) complexes in these inverse OLEDs are in turn used in the light-emitting layer, particularly preferably as a light-emitting layer without further additives.
  • the structure of inverse OLEDs and the materials usually used therein are known to the person skilled in the art.
  • Hhfac hexafluoroacetylacetone
  • Htta thienyltrifluoroacetone
  • Hqu 8-quinolinol
  • GdCI 3 x H 2 0 are commercially available and are used without further purification.
  • Gd (qu) 3 The production of Gd (qu) 3 is described in RG Charles et al. Spectrochim., Acta 8 (1956) 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne l'utilisation de complexes de gadolinium(III) en tant que molécules d'émission dans des diodes organiques électroluminescentes (OLED). Ces complexes présentent les formules (I) et (II) dans lesquelles les radicaux sont tels que définis dans les revendications et dans la description. La présente invention concerne également l'utilisation des complexes de gadolinium(III) sous forme de couche d'émission de lumière dans des diodes organiques électroluminescentes (OLED), une couche d'émission de lumière contenant au moins un complexe de gadolinium(III), une OLED contenant cette couche d'émission de lumière, ainsi que des dispositifs qui comprennent une telle OLED.
PCT/EP2004/014494 2003-12-19 2004-12-20 Utilisation de chelates de gadolinium(iii) servant de matieres luminescentes dans des diodes organiques electroluminescentes (oled) WO2005061655A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10360680A DE10360680A1 (de) 2003-12-19 2003-12-19 Verwendung von Gadolinium(III)-Chelaten als lumineszierende Materialien in organischen Leuchtdioden (OLEDs)
DE10360680.7 2003-12-19

Publications (1)

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WO2005061655A1 true WO2005061655A1 (fr) 2005-07-07

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PCT/EP2004/014494 WO2005061655A1 (fr) 2003-12-19 2004-12-20 Utilisation de chelates de gadolinium(iii) servant de matieres luminescentes dans des diodes organiques electroluminescentes (oled)

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DE (1) DE10360680A1 (fr)
WO (1) WO2005061655A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894164A (en) * 1973-03-15 1975-07-08 Rca Corp Chemical vapor deposition of luminescent films
EP1245659A1 (fr) * 2001-03-27 2002-10-02 Sumitomo Chemical Company, Limited Substance électroluminescente polymère et dispositif électroluminescent polymère l'utilisant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894164A (en) * 1973-03-15 1975-07-08 Rca Corp Chemical vapor deposition of luminescent films
EP1245659A1 (fr) * 2001-03-27 2002-10-02 Sumitomo Chemical Company, Limited Substance électroluminescente polymère et dispositif électroluminescent polymère l'utilisant

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