WO2004019348A1 - Layer configuration comprising an electron-blocking element - Google Patents

Layer configuration comprising an electron-blocking element Download PDF

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Publication number
WO2004019348A1
WO2004019348A1 PCT/EP2003/050344 EP0350344W WO2004019348A1 WO 2004019348 A1 WO2004019348 A1 WO 2004019348A1 EP 0350344 W EP0350344 W EP 0350344W WO 2004019348 A1 WO2004019348 A1 WO 2004019348A1
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Prior art keywords
layer configuration
acid
polymers
poly
layer
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PCT/EP2003/050344
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French (fr)
Inventor
Hieronymus Andriessen
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Agfa-Gevaert
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Priority to AU2003262548A priority Critical patent/AU2003262548A1/en
Publication of WO2004019348A1 publication Critical patent/WO2004019348A1/en

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    • 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
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7716—Chalcogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1416—Condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a layer configuration comprising an electron-blocking element.
  • US 4,175,982 discloses a photovoltaic device comprising a first, ohmic electrode and a second barrier electrode and sandwiched therebetween a photoactive layer comprising metal-free phthalocyanine dispersed in an electrically insulating binder, e.g. poly (N-vinyl carbazole) , polyvinylacetate, polycarbonate, polystyrene, polystyrene acrylonitrile copolymer and polyacrylonitrile, wherein the barrier electrode comprises a metal the oxide of which is electrically conductive.
  • an electrically insulating binder e.g. poly (N-vinyl carbazole) , polyvinylacetate, polycarbonate, polystyrene, polystyrene acrylonitrile copolymer and polyacrylonitrile
  • the barrier electrode comprises a metal the oxide of which is electrically conductive.
  • WO 00/06665 discloses an electroluminescent device comprising a light-emitting organic film, arranged between an anode material and a cathide material such that under an applied voltage, the device is forward biased and holes are injected from the anode material into the organic film adjacent to the anode material and electrons are injected from the cathode material into the organic film adjacent to the cathode material, resulting in light emission from the light-emitting organic film; wherein the device additionally comprises a solution-processed film of a blend of an acid-functional non-conductive polymer e.g. polymers having pendant groups selected from sulfonic acid, sulfinic acid, carboxylic acid,
  • an acid-functional non-conductive polymer e.g. polymers having pendant groups selected from sulfonic acid, sulfinic acid, carboxylic acid,
  • R is selected from hydrogen, C 1 -C 20 hydrocarbyl, hydroxy, alkoxy, and aryloxy, and a conductive polymer positioned between the anode material and the light-emitting organic film, wherein the weight ratio of non-conducting to conducting polymer is at least 0.75:1.
  • WO 00/0665 specifically discloses the following non- conductive polymers: sulfonated polyphenylenes, polyp enylenes bearing carboxylic acid functional groups, poly(styrene sulfonic acid), poly (2-acrylamido-2-methyl-l-propanesulfonic acid), polyacrylic acid, polymethacrylic acid or a mixture thereof.
  • WO 01/78464 discloses in an organic/polymer electroluminescent (EL) device which comprises: a transparent substrate; a semitransparent electrode deposited on the transparent substrate; a hole-injecting layer positioned on the semitransparent electrode; an emissive layer made of an organic EL-material, positioned on the hole-injecting layer; and electron-injecting layer positioned on the electron-injecting layer, the improvement comprising that single-ion conductors are employed for the hole-injecting layer and the electron-injecting layer.
  • EL organic/polymer electroluminescent
  • single-ion conductor which in plain language means a conductor of a single ion, although claim 9 teaches that the single ion conductor can be a single-cation conductor or a single anion conductor and claim 10 teaches that such single ion conductors can be represented as a general formula (I) or (II), comprising ether chain [(-CH 2 ) n O ⁇ ] such as polyethylene oxide or polypropylene oxide in the main chain, and contains anions such as SO 3 , COO or I in the main side chains
  • EO ethylene oxide
  • Non-EO non- ethylene oxide
  • PO propylene oxide
  • Non-PO represents
  • n a real number more than 0 and less than 1.
  • ionic polyurethane possesses good mechanical properties and high ionic conductivity with a single-ion transport character and that SIC s are generally of two different types: one is a polymer blend of an ionomer and polyether which usually possesses poor mechanical properties and the other is the copolymer of an oligomeric ionomer with polyether.
  • incorporation of the SIC s with soft and hard blocks into the EL devices dramatically improves not only luminance but also the efficiency and that SCC's possess electron-injecting and hole- blocking properties and SACs possess hole-injecting and electron- blocking properties .
  • a layer configuration on a support comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
  • a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid)
  • the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
  • Figure 1 is a schematic representation of a side view and a top view of the layer configuration used in devices 2 to 9, 11 to 16 and 18 to 26 and the circuit used for obtaining electroluminescence in which:
  • A represents a poly (ethylene terephthalate) support
  • C represents an electron blocking layer
  • D represents an electroluminescent layer containing ZnS:Cu nano- particles and a binder
  • E represents an evaporated aluminium electrode
  • F represents conductive silver paste dots for contacting
  • G represents IV-power source (Power Supply ES 030-5 of Delta
  • H electric conductive copper wire
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n- propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1, 1-dimethyl- propyl, 2 , 2-dimethylpropyl and 2-methyl-butyl etc.
  • aqueous for the purposes of the present invention means containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water- miscible organic solvents such as alcohols e.g.
  • glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
  • element as used in disclosing the present invention means a single layer containing one or more polymers selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) or two contiguous layers wherein the innermost layer of the element with respect to the support contains at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) and the outermost layer with respect to the support contains at least one polymer selected from the group consisting of polycarboxy- polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid, which is different from the polymers selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) in the innermost layer with respect to the support.
  • non-photoactive element as used in disclosing the present invention means an element which is not photoactive, where photoactive means either capable of reacting to light or capable of emitting light .
  • poly (3, 4-alkylenedioxythiophene) as used in disclosing the present invention means a polythiophene in which the 3 and 4 positions in the thiophene ring are linked by a -0- alkylene-O- group, where the term alkylene means a saturated hydrocarbon group containing the carbon atoms linking the two oxygen atoms in the -O-alkylene-0- group and also saturated hydrocarbon groups containing the carbon atoms linking the two oxygen atoms in the -O-alkylene-0- group in which these carbon atoms are covalently linked with one or more alkyl groups e.g. poly (3, 4-ethylenedioxythiophene) , poly [3, - (1, 2- propylene) dioxythiophene] and poly [3, 4- (1, 3-propylene) dioxy- thiophene] .
  • polycarboxy-polymer as used in disclosing the present invention means a polymer with more than one carboxylic acid group.
  • polysulfato-polymer as used in disclosing the present invention means a polymer with more than one hydrogen sulfate group .
  • polysulfo-polymer as used in disclosing the present invention means a polymer with more than one sulphonic acid groups .
  • polymer includes homopolymers, copolymers, terpolymers, graft polymers and block copolymers and both chain and condensation polymers .
  • the passage "material capable of transporting holes” as used in disclosing the present invention means a material into which holes can be injected and through which holes can be transported, such a material preferably having a hole mobility > 10 cm V s and particularly preferably having a hole mobility > 10 cm V s as measured by time of flight techniques or in a field effect transistor.
  • conductive polymer as used in disclosing present invention is a polymer in a state such that it has a specific conductivity of at least 10 S/cm and preferably a specific
  • HTs represents p-toluenesulphonic acid and Ts or tosylate represents p-toluenesulphonate .
  • a layer configuration on a support comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes.
  • Polyvinyphosphonic acid has the following formula: -(CH 2 CH) n -
  • the at least one polymer is a copolymer with a non-carboxy, non-amino, non-sulphato, non-sulpho, non-vinylphosphonic acid containing comonomer.
  • the thickness of the element is between 1 and 20 nm.
  • the at least one polymer is a copolymer with a non-carboxy, non-amino, non-sulphato, non-sulpho, non-vinylphosphonic acid containing comonomer and the thickness of the element is between 1 and 20 nm.
  • the element is exclusive of a conductive polymer.
  • the layer configuration is a transistor .
  • the element is preferably prepared by spincoating the coating or coatings from aqueous or solvent media. Solutions or dispersions for spincoating preferably have viscosities of about 2 to 3 cP meaning that up to 95% of the solution is spun off i.e. not deposited during the spincoating process. If the element is prepared by the application of two coatings the first coating is preferably dried in a drying cupboard before the second coating is applied. Depending upon the ingredients and solvents/dispersion media used in the two coatings the two coatings will form a single homogeneous layer after the second coating or two identifiable layers .
  • aspects of the present invention are realized with a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing a polycarboxy-polymer, the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
  • a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s the element containing a polycarboxy-polymer, the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
  • Polycarboxy-polymers may be vinylpolymers, condensation polymers or optionally modified natural products such as carbohydrates, e.g. carboxymethyl- cellulose and proteins, e.g. gelatin.
  • the polycarboxy-polymer is a polymer containing optionally substituted acrylic acid monomer units .
  • the polycarboxy-polymer is a polymer containing optionally substituted acrylic acid monomer units selected from the group consisting of: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid and citraconic acid.
  • the polycarboxy-polymer is polyacrylic acid or polymethacrylic acid.
  • Suitable polycarboxy-polymers include:
  • a layer configuration on a support comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing an optionally quaternized polyamine-polymer, the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
  • Optionally quaternized polyamine-polymers include both optionally quaternized aliphatic polyamine-polymers, e.g. polyallylamine hydrochloride and polymers with optionally quaternized nitrogen-containing heteroaromatic groups, e.g. homopolymers and copolymers of optionally substituted vinylpyridines, vinyldipyridyls, vinylquinolines,
  • vinylisoquinolines vinylacridines, vinylpyridazines, vinylpyrimidines, vinylpyrazines, vinyltriazine, vinylcinnolines, vinylphthalazines, vinylquinazolines, vinylquinoxalines, vinylpteridines, vinyloxadiazole and vinyloxazole .
  • the optionally quaternized polyamine-polymer is polyallylamine hydrochloride, an optionally quaternized polyvinylpyridine or a copolymer of an optionally quaternized vinyl pyridine.
  • the optionally quaternized polyamine-polymer is an optionally quaternized polyamine homopolymer, e.g. an optionally quaternized polyallylamine or an optionally quaternized polyvinylpyridine, and the thickness of the element is between 50 and 200 nm.
  • the optionally quaternized polyamine-polymer is an optionally quaternized polyamine copolymer, e.g. an optionally quaternized copolymer of vinyl pyridine, and the thickness of the element is between 1 and
  • Suitable polyamine-polymers include:
  • the element further contains a surfactant .
  • the element further contains a non-ionic surfactant e.g. ethoxylated/ fluoroalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluoroalkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants .
  • a non-ionic surfactant e.g. ethoxylated/ fluoroalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluoroalkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants .
  • Suitable non-ionic surfactants include:
  • Surfactant no. 01 ZONYLTM FSN, a 40% by weight solution of
  • Surfactant no. 03 ZONYLTM FS300, a 40% by weight aqueous solution of a fluorinated surfactant, from DuPont;
  • Surfactant no. 04 ZONYLTM FSO, a 50% by weight solution of a mixture of ethoxylated non-ionic fluoro- surfactant with the formula:
  • Surfactant no. 06 TegoglideTM 410, a polysiloxane-polymer copolymer surfactant, from Goldschmidt;
  • Surfactant no. 07 TegowetTM, a polysiloxane-polyester copolymer surfactant, from Goldschmidt;
  • Surfactant no. 08 FLUORADTMFC431 : CF 3 (CF 2 ) 7 S0 2 (C 2 H 5 ) -CH 2 CO-(OCH 2 CH 2 ) n OH from 3M;
  • Surfactant no. 09 FLUORADTMFC126, a mixture of the ammonium salts of perfluorocarboxylic acids, from 3M;
  • Surfactant no. 10 Polyoxyethylene-10-lauryl ether
  • Surfactant no. 11 FLUORADTMFC430, a 98.5% active fluoroaliphatic ester from 3M;
  • the element further contains an anionic surfactant.
  • anionic surfactants include:
  • Surfactant no. 12 ZONYLTM 7950, a fluorinated surfactant, from
  • Surfactant no. 13 ZONYLTM FSA, 25% by weight solution of
  • Surfactant no. 14 ZONYLTM FSE, a 14% by weight solution of
  • Surfactant no. 16 ZONYLTM FSP, a 35% by weight solution of
  • Surfactant no. 17 ZONYLTM UR: [F (CF 2 CF 2 ) ⁇ - 7 CH 2 CH 2 0j X P (0) (OH) y where x
  • Surfactant no. 18 ZONYLTM TBS: a 33% by weight solution of
  • Surfactant no. 19 ammonium salt of perfluoro-octanoic acid from 3M
  • the element further contains a binder.
  • the element further contains a cross-linking agent.
  • the layer configuration according to the present invention, the layer
  • 75 configuration further comprises a layer of an electroluminescent phosphor.
  • the layer configuration further comprises a layer of an electroluminescent
  • the electroluminescent phosphor belongs to the class of II-VI semiconductors e.g. ZnS, or is a combination of group II elements with oxidic anions, the most common being silicates, phosphates, carbonates, germanates, stannates, borates, vanadates, tungstates and oxysulphates .
  • Typical dopants are metals
  • the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with
  • the layer configuration further comprises a dielectric layer.
  • any dielectric material may be used in the dielectric layer, with yttria and barium titanate being preferred e.g. the barium titanate paste LUXPRINTTM type 7153E high K dielectric insulator 40 supplied by DuPont and the barium titanate paste ELECTRODAGTM EL-040 supplied by Acheson.
  • a positive ion exchanger may be incorporated into the dielectric layer to capture any ions dissolving escaping from the phosphor of the light-emitting layer.
  • the amount of ion exchanger in the dielectric layer has to be optimized so that it has a maximum effectiveness in reducing black spots while not reducing the initial brightness level. It is therefore preferred to add 0.5 to 50 parts by weight of ion exchanger to 100 parts by weight of the total amount of resin and dielectric material in the dielectric layer.
  • the ion exchanger may be organic or inorganic.
  • Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, salts of phosphoric acid and silicic acid and zeolite.
  • the support is transparent or translucent.
  • the support is paper, polymer film, glass or ceramic.
  • the support is a transparent or translucent polymer film.
  • a transparent or translucent support suitable for use with the electroconductive or antistatic layers, according to the present invention may be rigid or flexible and consist of a glass, a glass-polymer laminate, a polymer laminate, a thermoplastic polymer or a duroplastic polymer.
  • thin flexible supports are those made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, with poly (ethylene terephthalate) or poly (ethylene naphthalene-1, 4-dicarboxylate) being particularly preferred.
  • the layer configuration is an electroluminescent device.
  • the layer configuration is a light emitting diode.
  • Thin film electroluminescent devices are all characterized by one (or more) electroluminescent active layer (s) sandwiched between two electrodes .
  • a dielectric layer may also be part of the sandwich.
  • Thin film ELDs can be subdivided into organic and inorganic based ELDs.
  • Organic-based thin film ELDs can be subdivided into low molecular weight organic devices including oligomers (Organic Light Emitting Diodes (OLEDs) ) and high molecular weight organic devices (Polymer Light Emitting Diodes (PLEDs) .
  • the inorganic ELDs on the other hand can be further subdivided into the High Voltage Alternating Current (HV-AC) ELDs and the Low Voltage Direct Current (LV-DC) ELDs.
  • the LV-DC ELDs include Powder ELDs (DC-PEL Devices or DC-PELDs) and thin film DC-ELDs, hereinafter called Inorganic Light Emitting Diodes (ILEDs) .
  • the basic construction of organic ELDs comprises following layer arrangement : a transparent substrate (glass or flexible plastic), a transparent conductor, e.g. Indium Tin Oxide (ITO) , a hole transporting layer, a luminescent layer, and a second electrode, e.g. a Ca, Mg/Ag or Al/Li electrode.
  • a transparent substrate glass or flexible plastic
  • ITO Indium Tin Oxide
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer and the luminescent layer are 10- 50 nm thick and applied by vacuum deposition
  • the hole transporting layer is usually about 40 nm thick and the luminescent layer is usually about 100 nm thick and applied by spin coating or other non-vacuum coating techniques.
  • a direct voltage of 5 - 10 V is applied between both electrodes and light emission results from holes and electrons being injected from the positive and negative electrodes respectively combining in the luminescent layer thereby producing the energy to excite the lumi
  • the hole transporting layer and electroluminescent layer consist of low molecular organic compounds, N, N' -diphenyl- 1, 1' -biphenyl-4 , 4' -diamine (TPD) can, for example be used as the hole transporter and aluminium (III) 8-hydroxyquinoline complex ( lq 3 ) , polyaromatics (anthracene derivatives, perylene derivatives and stilbene derivatives) and polyhetero-aromatics (oxazoles, oxadiazoles, thiazoles etc.) can be used as electroluminescent compounds .
  • N, N' -diphenyl- 1, 1' -biphenyl-4 , 4' -diamine TPD
  • TPD hole transporter and aluminium (III) 8-hydroxyquinoline complex
  • polyaromatics anthracene derivatives, perylene derivatives and stilbene derivatives
  • polyhetero-aromatics oxazoles, oxadia
  • electroluminescent compounds that can be used are polymers like the non-conjugated polyvinylcarbazole derivatives (PVK) or conjugated polymers like poly (p-phenylene vinylenes) (PPV) , polyfluorenes, poly (3-alkylthiophene) , pol (p-phenylene ethynylenes) etc. These high-molecular-weigth materials allow for the easy preparation of thin films by casting, and show a high resistance to crystallization.
  • Low voltage DC PEL Devices generally comprise a transparent substrate, a transparent conductor (ITO) , a doped ZnS phosphor layer (20 ⁇ m) , and a top electrode of evaporated aluminium.
  • the phosphor layer is applied by means of the doctor blade technique or screen printing on an ITO conducting layer. Subsequently an aluminium electrode is applied by evaporation. Upon applying a direct current voltage of several volts (ITO positive) , holes start moving towards the aluminium electrode, thereby creating an insulating region (about 1 ⁇ m in thickness) next to the ITO layer within one minute or so. This results in a current drop which is associated with the onset of light emission. This process has been called the forming process. In the thin high resistive phosphor layer thereby formed, high electric fields occur and electroluminescence is already possible at low voltages (typically between 10 and 30 V) . Que et al . [see Appl . Phys. Lett., volume 73, pages 2727-2729 (1998)] using ZnS : Cu nano crystals achieved turn on voltages of below 5 V.
  • hybrid LEDs inorganic emitting so-called quantum dots are used in combination with organic polymers with charge transporting properties and in some cases also emitting properties.
  • Hybrid LEDs with CdSe nano particles have been reported by Colvin et al . [see Nature, volume 370, pages 354-357, (1994)], Dabbousi et al . [see Appl. Phys. Lett., volume 66, pages 1316-1318 (1995), and Gao et al. [see J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)]; and with ZnS : Cu nano crystals have been reported by Huang et al . [see Appl. Phys. Lett., volume 70, pages 2335-2337 (1997)] all included herein by reference.
  • the layer configuration is a photovoltaic device.
  • the layer configuration further comprises at least one photovoltaic layer.
  • the photovoltaic layer may be organic layer, a hybrid inorganic and organic layer or an inorganic layer.
  • the layer configuration is a solar cell.
  • Photovoltaic devices incorporating the layer configuration, according to the present invention can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode.
  • the hole transporting medium may be a liquid electrolyte supporting a redox reaction, a gel electrolyte supporting a redox reaction, an organic hole transporting material, which may be a low molecular weight material such as 2, 2 ' , 7, 7 ' -tetrakis (N, N-di-p-methoxyphenyl- amine) 9, 9' -spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, poly (N-vinylcarbazole) etc., or inorganic semiconductors such as Cul, CuSCN etc.
  • the charge transporting process can be ionic as in the case of a liquid electrolyte or gel electrolyte or electronic as in the case of organic or inorganic hole transporting materials.
  • Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types : structures which receive light from both sides and those which receive light from one side.
  • An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer.
  • Such devices preferably have their sides sealed with a polymer, an adhesive or other means to prevent deterioration or volatilization of the inside substances.
  • the external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known.
  • Organic photovoltaic layers of the layer configuration, according to the present invention are, for example, mixtures of fullerene molecules (as electron acceptor and electron transporter) with conjugated polymers (e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter) [see Brabec et al . , Adv. Funct. Mater., volume 11(1), pages 15 - 26 (2001)]. In 1995 Halls et al . reported in Nature, volume 376, page 498 the successful use of acceptor-type conjugated polymers instead of fullerenes .
  • conjugated polymers e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter)
  • the layer configuration can be incorporated in hybrid photovoltaic compositions such as described in 1991 by Graetzel et al . in Nature, volume 353, pages 737-740, in 1998 by U. Bach et al . [see Nature, volume 395, pages 583-585 (1998)] and in 2002 by W. U. Huynh et al . [see Science, volume 295, pages 2425-2427 (2002)].
  • at least one of the components is inorganic (e.g. nano- Ti ⁇ 2 as electron transporter, CdSe as light absorber and electron transporter) and at least one of the components is organic (e.g. triphenylamine as hole transporter or poly (3-hexylthiophene) as hole transporter) .
  • Inorganic photovoltaic layers which can be used in the layer configuration according to this invention are described in EP-A 1 176 646.
  • the layer configuration further comprises a layer with one or more of the electron transporting or hole transporting components described above, but within such a configuration that it can be used as a transistor.
  • the semiconductor can be n-type, p-type or both (ambipolar transistor) and can be either organic or inorganic.
  • Layer configurations comprising an element, according to the present invention, between a positive electrode and a material capable of hole transport and capable of reducing hole-electron recombination at the positive electrode can be used in a wide range of electronic devices such as photovoltaic devices, solar cells, batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, sensors for organic and bio-organic materials and field effect transistors [see also chapter 10 of the Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, Weinheim (1999)].
  • the invention is illustrated hereinafter by way of reference light emitting devices and light emitting devices according to the present invention.
  • the percentages and ratios given in these examples are by weight unless otherwise indicated.
  • CelquatTM SC240C a cationic p-saccharide from National Starch and Chemical
  • CelquatTM L200 a cationic cellulose from National Starch and Chemical
  • Solutions 1 and 2 at room temperature were added simultaneously both at a flow rate of 500 mL/min to solution 3, held at room temperature and stirred at 1500 rpm for 60 s.
  • 1000 mL of the resulting dispersion 1000 mL of a 1% polyphosphoric acid solution adjusted to pH 6 with ammonium hydroxide was added and the dispersion was concentrated to 1000 mL by means ultrafiltration using a Fresenius F60 cartridge. This dispersion was subsequently diafiltered by using 5500 mL of a 1% solution of polyphosphoric acid solution adjusted to pH 6 with ammonium hydroxide solution in water.
  • the dispersion was further concentrated to a volume of about 570 mL to produce an aqueous dispersion at pH 6 containing 30g/L ZnS:Cu and 1% polyphosphoric acid.
  • the dispersion was then ball- milled for 1 hour.
  • 20 mL of the resulting dispersion was then ultrasonically treated with a ultrasound bar (Vibra cell VCX 400 W from Sonics & Materials Inc. - amplitude about 78% - output 40%) for 3 minutes while cooling in ice.
  • 3.2 g of a 5% by weight aqueous solution of poly (vinylpyrrolidone) in water was then added to 16.8 g of the ZnS:Cu dispersion followed by further ultrasonic treatment with the ultrasound bar for 5 minutes.
  • ITO indium tin oxide
  • PET poly (ethylene terephthalate)
  • Solutions 4, 6, 8 and 10 were spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s. This resulted in 10 an element thickness of about 5 to 10 nm. The substrates for devices 2, 4, 6 and 8 were thereby produced.
  • Solutions 5, 7, 9 and 11 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s. This resulted in an element thickness of about 100 nm thereby producing 75 the substrates for devices 3, 5, 7 and 9 respectively.
  • the thicknesses were measured with a DEKTAKTM profilometer with the element spincoated on glass. Similar element thicknesses can be expected on ITO/PET.
  • the electroluminescent nano ZnS : Cu-dispersion was spincoated at 1000 rpm for 6 s and then at 2000 rpm for 50 s on the substrates of devices 1 to 9, device 1 without an elctron blocking element and devices 2 to 9 with the above-described electron blocking elements.
  • the resulting electroluminescent ZnS : Cu-layers were then dried at
  • the lifetime of the light emitting device was taken to be the time between the application of the optimum voltage and the moment no further electroluminescence could be observed.
  • the optimum voltage was that voltage at which maximum light output was observed. Table 2
  • Devices 10 to 16 were prepared as described for Devices 1 to 9 except that the patterned ITO electrode was coated with elements incorporating PAP-01. Solutions 12 to 17, used for preparing these elements, prepared as described for Solutions 1 to 11, are given below in Table 3.
  • Solutions 12 and 13 were spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 1500 rpm for 50 s and the element dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm, thereby producing the substrates for device 11 and 12 respectively.
  • Solutions 14, 15, 16 and 17 were spincoated on a patterned ITO/PET sheet at 800 rpm for 6 s and then at 4000 rpm for 50 s and the element dried at 40 °C for 10 minutes. This resulted in element thicknesses of about 5 to 10 nm, thereby producing the substrates for devices 13, 14, 15 and 16 respectively.
  • the performance of the devices is dependent upon the acid used to at least partially quaternize the polyamine-polymers.
  • PAP-03 there was an improvement for 5 nm elements in the case of quaternization with p-toluenesulphonic acid and hydrobromic acid.
  • PAP-04 there was an improvement for 5 nm elements in the case of quaternization with p-toluenesulphonic acid and hydrochloric acid.
  • Devices 18 and 19 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating poly (vinyl phosphonic acid) . Solutions 18 and 19, used for preparing these elements, prepared as described for Solutions 4 to 11, are given below in Table 5.
  • Solution 18 was spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in an element thickness of about 5 to 10 nm, thereby producing the substrate for device 18.
  • Solution 19 was spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in an element thickness of about 100 nm, thereby producing the substrate for device 19.
  • devices with 5 nm and 100 nm poly (vinylphosphonic acid) elements exhibited a decrease in lifetime between element thicknesses of 5 nm and 100 nm.
  • Devices 20 to 22 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating polyacrylamide . Solutions 20 and 21, used for preparing these elements, prepared as described for Solutions 4 to 11, are given below in Table 7.
  • Solution 20 was spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40 °C for 10 minutes. This resulted in an element thickness of about 5 to 10 nm, thereby producing the substrate for device 21.
  • Solution 21 was spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40 °C for 10 minutes. This resulted in an element thickness of about 100 nm, thereby producing the substrate for device 22. Performance of the light emitting devices
  • Devices 23 to 26 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating polyacrylamide. Solutions 22 to 25, used for preparing these elements, prepared as described for Solutions 1 to 11, are given below in Table 9.
  • Solutions 23 and 25 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm, thereby producing the substrates for devices 24 and 26 respectively.
  • the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.

Abstract

A layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly(3,4-alkylenedioxythiophene)s, the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly(vinylphosphonic acid), the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes.

Description

LAYER CONFIGURATION COMPRISING AN ELECTRON-BLOCKING ELEMENT
Field of the invention
The present invention relates to a layer configuration comprising an electron-blocking element.
Background of the invention.
US 4,175,982 discloses a photovoltaic device comprising a first, ohmic electrode and a second barrier electrode and sandwiched therebetween a photoactive layer comprising metal-free phthalocyanine dispersed in an electrically insulating binder, e.g. poly (N-vinyl carbazole) , polyvinylacetate, polycarbonate, polystyrene, polystyrene acrylonitrile copolymer and polyacrylonitrile, wherein the barrier electrode comprises a metal the oxide of which is electrically conductive.
WO 00/06665 discloses an electroluminescent device comprising a light-emitting organic film, arranged between an anode material and a cathide material such that under an applied voltage, the device is forward biased and holes are injected from the anode material into the organic film adjacent to the anode material and electrons are injected from the cathode material into the organic film adjacent to the cathode material, resulting in light emission from the light-emitting organic film; wherein the device additionally comprises a solution-processed film of a blend of an acid-functional non-conductive polymer e.g. polymers having pendant groups selected from sulfonic acid, sulfinic acid, carboxylic acid,
2 phosphoric acid, phosphomc acid, phosphmic acid, and -N+ (R) H where R is selected from hydrogen, C1-C20 hydrocarbyl, hydroxy, alkoxy, and aryloxy, and a conductive polymer positioned between the anode material and the light-emitting organic film, wherein the weight ratio of non-conducting to conducting polymer is at least 0.75:1. WO 00/0665 specifically discloses the following non- conductive polymers: sulfonated polyphenylenes, polyp enylenes bearing carboxylic acid functional groups, poly(styrene sulfonic acid), poly (2-acrylamido-2-methyl-l-propanesulfonic acid), polyacrylic acid, polymethacrylic acid or a mixture thereof.
WO 01/78464 discloses in an organic/polymer electroluminescent (EL) device which comprises: a transparent substrate; a semitransparent electrode deposited on the transparent substrate; a hole-injecting layer positioned on the semitransparent electrode; an emissive layer made of an organic EL-material, positioned on the hole-injecting layer; and electron-injecting layer positioned on the electron-injecting layer, the improvement comprising that single-ion conductors are employed for the hole-injecting layer and the electron-injecting layer. The specification does not define the meaning of the term "single-ion conductor", which in plain language means a conductor of a single ion, although claim 9 teaches that the single ion conductor can be a single-cation conductor or a single anion conductor and claim 10 teaches that such single ion conductors can be represented as a general formula (I) or (II), comprising ether chain [(-CH2)nO~] such as polyethylene oxide or polypropylene oxide in the main chain, and contains anions such as SO3 , COO or I in the main side chains
+ , + 2+ that form ionic bonds with counter ions such as Na , Li , Zn , Mg , Eu , or (NH3) 4 :
-(-EO-) m-(-NonEO-) n-
(I)
A C
(-PO- -NonPO-
( i i :
A C
wherein, EO represents ethylene oxide; Non-EO represents non- ethylene oxide; PO represents propylene oxide; Non-PO represents
- + non-propylene oxide; A represents anion; C represents cation; m+n=ll and n represents a real number more than 0 and less than 1.
In 2001 T.-W. Lee and 0. 0. Park disclosed in Advanced Materials, volume 13, pages 1274-1278, polymer light-emitting energy-well devices using single-ion conductors (SIC's) in which charge injection and its confinement simultaneously in EL devices is striven for by using both a single-cationic conductor (SCC) and a single-anionic conductor (SAC) , which "greatly improve the charge injection due to accumulation of the mobile ions near the electrodes" with the aim of "confining well-electrons and holes leading to enhanced recombination rate of the pairs" in devices in which "the mobile ions to play a key role in improvement of charge injection are separately located near both electrodes in the structure of a sandwiched multi-layer device instead of blending with the emitting material so that the problem of phase separation of the emitting materials can be avoided" . They further disclose that ionic polyurethane possesses good mechanical properties and high ionic conductivity with a single-ion transport character and that SIC s are generally of two different types: one is a polymer blend of an ionomer and polyether which usually possesses poor mechanical properties and the other is the copolymer of an oligomeric ionomer with polyether. They also disclosed that incorporation of the SIC s with soft and hard blocks into the EL devices dramatically improves not only luminance but also the efficiency and that SCC's possess electron-injecting and hole- blocking properties and SACs possess hole-injecting and electron- blocking properties .
In 2001 T.-W. Lee et al . disclosed in Journal of Applied Physics, volume 90, pages 2128-2134, a study of the effect of ion concentration, neutralization level and counterions in ionomers to obtain the optimal electroluminescent (EL) characteristics in polymer light-emitting diodes using pol [2-methoxy-5- (2' -ethyl- hexyloxy) -1, 4-phenylenevinylene] (MEH-PPV) for the emissive layer and sulphonated polystyrene (SPS) ionomers for the electron- injecting layer. A general problem in electronic devices, particularly in light emitting diodes, is undesirable hole-electron recombination at the positive electrode thereby reducing the efficiency and lifetime of the device.
Aspects of the invention.
It is therefore an aspect of the present invention to provide an element between a positive electrode and a material capable of hole transport, which is capable of reducing hole-electron recombination at the positive electrode thereby increasing the efficiency and lifetime of electronic devices containing such layer configurations .
Further aspects and advantages of the invention will become apparent from the description hereinafter.
Summary of the invention
It has been surprisingly found that the use of an element containing an organic polymer containing covalently bonded sulphonic acid groups, sulphate groups, carboxy groups, optionally quaternized amine groups or phosphonic acid groups between a positive electrode and a material capable of hole transport improves the device performance by increasing the lifetime.
Aspects of the present invention are realized by a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
Preferred embodiments are disclosed in the dependent claims.
Detailed description of the invention.
Figure 1 is a schematic representation of a side view and a top view of the layer configuration used in devices 2 to 9, 11 to 16 and 18 to 26 and the circuit used for obtaining electroluminescence in which:
A represents a poly (ethylene terephthalate) support;
B represents an sputtered ITO layer;
C represents an electron blocking layer;
D represents an electroluminescent layer containing ZnS:Cu nano- particles and a binder;
E represents an evaporated aluminium electrode
F represents conductive silver paste dots for contacting
G represents IV-power source (Power Supply ES 030-5 of Delta
Elektronica)
H represents electric conductive copper wires
I indicates the first layer
II indicates the second layer
III indicates the third layer
Definitions
The term alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n- propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1, 1-dimethyl- propyl, 2 , 2-dimethylpropyl and 2-methyl-butyl etc. The term aqueous for the purposes of the present invention means containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water- miscible organic solvents such as alcohols e.g. methanol, ethanol,ι 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc. The term element as used in disclosing the present invention means a single layer containing one or more polymers selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) or two contiguous layers wherein the innermost layer of the element with respect to the support contains at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) and the outermost layer with respect to the support contains at least one polymer selected from the group consisting of polycarboxy- polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid, which is different from the polymers selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) in the innermost layer with respect to the support.
The term "non-photoactive element" as used in disclosing the present invention means an element which is not photoactive, where photoactive means either capable of reacting to light or capable of emitting light .
The term poly (3, 4-alkylenedioxythiophene) as used in disclosing the present invention means a polythiophene in which the 3 and 4 positions in the thiophene ring are linked by a -0- alkylene-O- group, where the term alkylene means a saturated hydrocarbon group containing the carbon atoms linking the two oxygen atoms in the -O-alkylene-0- group and also saturated hydrocarbon groups containing the carbon atoms linking the two oxygen atoms in the -O-alkylene-0- group in which these carbon atoms are covalently linked with one or more alkyl groups e.g. poly (3, 4-ethylenedioxythiophene) , poly [3, - (1, 2- propylene) dioxythiophene] and poly [3, 4- (1, 3-propylene) dioxy- thiophene] .
The term polycarboxy-polymer as used in disclosing the present invention means a polymer with more than one carboxylic acid group. The term polysulfato-polymer as used in disclosing the present invention means a polymer with more than one hydrogen sulfate group .
The term polysulfo-polymer as used in disclosing the present invention means a polymer with more than one sulphonic acid groups .
The term polymer includes homopolymers, copolymers, terpolymers, graft polymers and block copolymers and both chain and condensation polymers .
The passage "material capable of transporting holes" as used in disclosing the present invention means a material into which holes can be injected and through which holes can be transported, such a material preferably having a hole mobility > 10 cm V s and particularly preferably having a hole mobility > 10 cm V s as measured by time of flight techniques or in a field effect transistor.
The term conductive polymer as used in disclosing present invention is a polymer in a state such that it has a specific conductivity of at least 10 S/cm and preferably a specific
-4 conductivity of at least 10 S/cm. The abbreviation HTs represents p-toluenesulphonic acid and Ts or tosylate represents p-toluenesulphonate .
Layer configuration
Aspects of the present invention are realized with a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes. Polyvinyphosphonic acid has the following formula: -(CH2CH)n-
HO-P=0
OH and is supplied by Hoechst .
According to a first embodiment of the layer configuration, according to the present invention, the at least one polymer is a copolymer with a non-carboxy, non-amino, non-sulphato, non-sulpho, non-vinylphosphonic acid containing comonomer.
According to a second embodiment of the layer configuration, according to the present invention, the thickness of the element is between 1 and 20 nm.
According to a third embodiment of the layer configuration, according to the present invention, the at least one polymer is a copolymer with a non-carboxy, non-amino, non-sulphato, non-sulpho, non-vinylphosphonic acid containing comonomer and the thickness of the element is between 1 and 20 nm.
According to a fourth embodiment of the layer configuration, according to the present invention, the element is exclusive of a conductive polymer.
According to a fifth embodiment of the layer configuration, according to the present invention, the layer configuration is a transistor .
The element is preferably prepared by spincoating the coating or coatings from aqueous or solvent media. Solutions or dispersions for spincoating preferably have viscosities of about 2 to 3 cP meaning that up to 95% of the solution is spun off i.e. not deposited during the spincoating process. If the element is prepared by the application of two coatings the first coating is preferably dried in a drying cupboard before the second coating is applied. Depending upon the ingredients and solvents/dispersion media used in the two coatings the two coatings will form a single homogeneous layer after the second coating or two identifiable layers .
Polycarboxy-polymers
Aspects of the present invention are realized with a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing a polycarboxy-polymer, the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
Polycarboxy-polymers, according to the present invention, may be vinylpolymers, condensation polymers or optionally modified natural products such as carbohydrates, e.g. carboxymethyl- cellulose and proteins, e.g. gelatin. According to a sixth embodiment of the layer configuration, according to the present invention, the polycarboxy-polymer is a polymer containing optionally substituted acrylic acid monomer units . According to a seventh embodiment of the layer configuration, according to the present invention, the polycarboxy-polymer is a polymer containing optionally substituted acrylic acid monomer units selected from the group consisting of: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid and citraconic acid.
According to an eighth embodiment of the layer configuration, according to the present invention, the polycarboxy-polymer is polyacrylic acid or polymethacrylic acid.
Suitable polycarboxy-polymers include:
Figure imgf000009_0001
Polyamine-polymers
Aspects of the present invention are realized by a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s, the element containing an optionally quaternized polyamine-polymer, the surface of one side of the element being contiguous with a positive electrode and the surface on the opposite side of the element being contiguous with a material capable of transporting holes .
Optionally quaternized polyamine-polymers include both optionally quaternized aliphatic polyamine-polymers, e.g. polyallylamine hydrochloride and polymers with optionally quaternized nitrogen-containing heteroaromatic groups, e.g. homopolymers and copolymers of optionally substituted vinylpyridines, vinyldipyridyls, vinylquinolines,
5 vinylisoquinolines, vinylacridines, vinylpyridazines, vinylpyrimidines, vinylpyrazines, vinyltriazine, vinylcinnolines, vinylphthalazines, vinylquinazolines, vinylquinoxalines, vinylpteridines, vinyloxadiazole and vinyloxazole .
According to a ninth embodiment of the layer configuration,
10 according to the present invention, the optionally quaternized polyamine-polymer is polyallylamine hydrochloride, an optionally quaternized polyvinylpyridine or a copolymer of an optionally quaternized vinyl pyridine.
According to a tenth embodiment of the layer configuration,
75 according to the present invention, the optionally quaternized polyamine-polymer is an optionally quaternized polyamine homopolymer, e.g. an optionally quaternized polyallylamine or an optionally quaternized polyvinylpyridine, and the thickness of the element is between 50 and 200 nm.
20 According to an eleventh embodiment of the layer configuration, according to the present invention, the optionally quaternized polyamine-polymer is an optionally quaternized polyamine copolymer, e.g. an optionally quaternized copolymer of vinyl pyridine, and the thickness of the element is between 1 and
25 20 nm .
Suitable polyamine-polymers, according to the present invention, include:
Figure imgf000010_0001
Figure imgf000011_0001
Surfactants
According to a twelfth embodiment of the layer configuration, according to the present invention, the element further contains a surfactant .
According to a thirteenth embodiment of the layer configuration, according to the present invention, the element further contains a non-ionic surfactant e.g. ethoxylated/ fluoroalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluoroalkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants .
Suitable non-ionic surfactants include:
Surfactant no. 01 = ZONYL™ FSN, a 40% by weight solution of
F (CF2CF2)ι-9CH2CH2θ(CH2CH2θ)xH in a 50% by weight solution of isopropanol in water where x = 0 to about 25, from DuPont;
Surfactant no. 02 = ZONYL™ FSN-100: F (CF2CF2) ι-gCH2CH20 (CH2CH20) XH where x = 0 to about 25, from DuPont;
Surfactant no. 03 = ZONYL™ FS300, a 40% by weight aqueous solution of a fluorinated surfactant, from DuPont;
Surfactant no. 04 = ZONYL™ FSO, a 50% by weight solution of a mixture of ethoxylated non-ionic fluoro- surfactant with the formula:
F(CF2CF2) 1-7CH2CH2θ(CH2CH20)yH where y = 0 to ca . 15 in a 50% by weight solution of ethylene glycol in water, from DuPont;
Surfactant no. 05 = ZONYL™ FSO-100, a mixture of ethoxylated non- ionic fluoro-surfactant from DuPont with the formula: F (CF2CF2) ι-7CH2CH20 (CH2CH20) yH where y = 0 to ca. 15 from DuPont;
Surfactant no. 06 = Tegoglide™ 410, a polysiloxane-polymer copolymer surfactant, from Goldschmidt;
Surfactant no. 07 = Tegowet™, a polysiloxane-polyester copolymer surfactant, from Goldschmidt; Surfactant no. 08 = FLUORAD™FC431 : CF3(CF2)7S02(C2H5) -CH2CO-(OCH2CH2)nOH from 3M; Surfactant no. 09 = FLUORAD™FC126, a mixture of the ammonium salts of perfluorocarboxylic acids, from 3M; Surfactant no. 10 = Polyoxyethylene-10-lauryl ether Surfactant no. 11 = FLUORAD™FC430, a 98.5% active fluoroaliphatic ester from 3M;
According to a fourteenth embodiment of the layer configuration, according to the present invention, the element further contains an anionic surfactant. Suitable anionic surfactants include:
Surfactant no. 12 = ZONYL™ 7950, a fluorinated surfactant, from
DuPont;
Surfactant no. 13 = ZONYL™ FSA, 25% by weight solution of
F(CF2CF2) ι-9CH2CH2SCH2CH2COOLi in a 50% by weight solution of isopropanol in water, from DuPont;
Surfactant no. 14 = ZONYL™ FSE, a 14% by weight solution of
[F(CF2CF2)ι-7CH2CH2θ]xP(0) (0NH )y where x = 1 or 2; y = 2 or 1; and x + y = 3 in a 70% by weight solution of ethylene glycol in water, from DuPont;
Surfactant no. 15 = ZONYL™ FSJ, a 40% by weight solution of a blend of F(CF2CF2) ι-7CH2CH20]xP (0) (ONH )y where x = 1 or 2; y = 2 or 1; and x + y = 3 with a hydrocarbon surfactant in 25% by weight solution of isopropanol in water, from DuPont;
Surfactant no. 16 = ZONYL™ FSP, a 35% by weight solution of
[F(CF2CF2)1_7CH2CH20]XP(0) (ONH )y where x = 1 or 2; y = 2 or 1 and x + y = 3 in 69.2% by weight solution of isopropanol in water, from DuPont;
Surfactant no. 17 = ZONYL™ UR: [F (CF2CF2) ι-7CH2CH20j XP (0) (OH) y where x
= 1 or 2; y = 2 or 1 and x + y = 3, from DuPont;
Surfactant no. 18 = ZONYL™ TBS: a 33% by weight solution of
F(CF CF2) 3-8CH2CH2SO3H in a 4.5% by weight solution of acetic acid in water, from DuPont;
Surfactant no. 19 = ammonium salt of perfluoro-octanoic acid from 3M
Binder According to a fifteenth embodiment of the layer configuration, according to the present invention, the element further contains a binder.
Crosslinking agent
According to a sixteenth embodiment of the layer configuration, according to the present invention, the element further contains a cross-linking agent.
10
Electroluminescent phosphors
According to a seventeenth embodiment of the layer configuration, according to the present invention, the layer
75 configuration further comprises a layer of an electroluminescent phosphor.
According to an eighteenth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent
20 phosphor, wherein the electroluminescent phosphor belongs to the class of II-VI semiconductors e.g. ZnS, or is a combination of group II elements with oxidic anions, the most common being silicates, phosphates, carbonates, germanates, stannates, borates, vanadates, tungstates and oxysulphates . Typical dopants are metals
25 and all the rare earths e.g. Cu, Ag, Mn, Eu, Sm, Tb and Ce . According to a nineteenth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with
30 manganese, copper or terbium, or CaGa2S4 doped with cerium.
Dielectric layer
According to a twentieth embodiment of the layer 35 configuration, according to the present invention, the layer configuration further comprises a dielectric layer.
Any dielectric material may be used in the dielectric layer, with yttria and barium titanate being preferred e.g. the barium titanate paste LUXPRINT™ type 7153E high K dielectric insulator 40 supplied by DuPont and the barium titanate paste ELECTRODAG™ EL-040 supplied by Acheson. A positive ion exchanger may be incorporated into the dielectric layer to capture any ions dissolving escaping from the phosphor of the light-emitting layer. The amount of ion exchanger in the dielectric layer has to be optimized so that it has a maximum effectiveness in reducing black spots while not reducing the initial brightness level. It is therefore preferred to add 0.5 to 50 parts by weight of ion exchanger to 100 parts by weight of the total amount of resin and dielectric material in the dielectric layer. The ion exchanger may be organic or inorganic.
Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, salts of phosphoric acid and silicic acid and zeolite.
Support
According to a twenty-first embodiment of the layer configuration, according to the present invention, the support is transparent or translucent.
According to a twenty-second embodiment of the layer configuration, according to the present invention, the support is paper, polymer film, glass or ceramic. According to a twenty-third embodiment of the layer configuration, according to the present invention, the support is a transparent or translucent polymer film.
A transparent or translucent support suitable for use with the electroconductive or antistatic layers, according to the present invention, may be rigid or flexible and consist of a glass, a glass-polymer laminate, a polymer laminate, a thermoplastic polymer or a duroplastic polymer. Examples of thin flexible supports are those made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, with poly (ethylene terephthalate) or poly (ethylene naphthalene-1, 4-dicarboxylate) being particularly preferred.
Electroluminescent devices
According to a twenty-fourth embodiment of the layer configuration, according to the present invention, the layer configuration is an electroluminescent device.
According to a twenty-fifth embodiment of the layer configuration, according to the present invention, the layer configuration is a light emitting diode.
Thin film electroluminescent devices (ELDs) are all characterized by one (or more) electroluminescent active layer (s) sandwiched between two electrodes . Optionally a dielectric layer may also be part of the sandwich.
Thin film ELDs can be subdivided into organic and inorganic based ELDs. Organic-based thin film ELDs can be subdivided into low molecular weight organic devices including oligomers (Organic Light Emitting Diodes (OLEDs) ) and high molecular weight organic devices (Polymer Light Emitting Diodes (PLEDs) . The inorganic ELDs on the other hand can be further subdivided into the High Voltage Alternating Current (HV-AC) ELDs and the Low Voltage Direct Current (LV-DC) ELDs. The LV-DC ELDs include Powder ELDs (DC-PEL Devices or DC-PELDs) and thin film DC-ELDs, hereinafter called Inorganic Light Emitting Diodes (ILEDs) .
The basic construction of organic ELDs (PLED and OLED) comprises following layer arrangement : a transparent substrate (glass or flexible plastic), a transparent conductor, e.g. Indium Tin Oxide (ITO) , a hole transporting layer, a luminescent layer, and a second electrode, e.g. a Ca, Mg/Ag or Al/Li electrode. For OLEDs the hole transporting layer and the luminescent layer are 10- 50 nm thick and applied by vacuum deposition, whereas for PLEDs the hole transporting layer is usually about 40 nm thick and the luminescent layer is usually about 100 nm thick and applied by spin coating or other non-vacuum coating techniques. A direct voltage of 5 - 10 V is applied between both electrodes and light emission results from holes and electrons being injected from the positive and negative electrodes respectively combining in the luminescent layer thereby producing the energy to excite the luminescent species to emit light.
In OLEDs the hole transporting layer and electroluminescent layer consist of low molecular organic compounds, N, N' -diphenyl- 1, 1' -biphenyl-4 , 4' -diamine (TPD) can, for example be used as the hole transporter and aluminium (III) 8-hydroxyquinoline complex ( lq3) , polyaromatics (anthracene derivatives, perylene derivatives and stilbene derivatives) and polyhetero-aromatics (oxazoles, oxadiazoles, thiazoles etc.) can be used as electroluminescent compounds .
In PLEDs electroluminescent compounds that can be used are polymers like the non-conjugated polyvinylcarbazole derivatives (PVK) or conjugated polymers like poly (p-phenylene vinylenes) (PPV) , polyfluorenes, poly (3-alkylthiophene) , pol (p-phenylene ethynylenes) etc. These high-molecular-weigth materials allow for the easy preparation of thin films by casting, and show a high resistance to crystallization. Low voltage DC PEL Devices generally comprise a transparent substrate, a transparent conductor (ITO) , a doped ZnS phosphor layer (20μm) , and a top electrode of evaporated aluminium. The phosphor layer is applied by means of the doctor blade technique or screen printing on an ITO conducting layer. Subsequently an aluminium electrode is applied by evaporation. Upon applying a direct current voltage of several volts (ITO positive) , holes start moving towards the aluminium electrode, thereby creating an insulating region (about 1 μm in thickness) next to the ITO layer within one minute or so. This results in a current drop which is associated with the onset of light emission. This process has been called the forming process. In the thin high resistive phosphor layer thereby formed, high electric fields occur and electroluminescence is already possible at low voltages (typically between 10 and 30 V) . Que et al . [see Appl . Phys. Lett., volume 73, pages 2727-2729 (1998)] using ZnS : Cu nano crystals achieved turn on voltages of below 5 V.
In hybrid LEDs, inorganic emitting so-called quantum dots are used in combination with organic polymers with charge transporting properties and in some cases also emitting properties. Hybrid LEDs with CdSe nano particles have been reported by Colvin et al . [see Nature, volume 370, pages 354-357, (1994)], Dabbousi et al . [see Appl. Phys. Lett., volume 66, pages 1316-1318 (1995), and Gao et al. [see J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)]; and with ZnS : Cu nano crystals have been reported by Huang et al . [see Appl. Phys. Lett., volume 70, pages 2335-2337 (1997)] all included herein by reference.
Photovoltaic devices
According to a twenty-sixth embodiment of the layer configuration, according to the present invention, the layer configuration is a photovoltaic device.
According to a twenty-seventh embodiment of the layer configuration, according to the present invention, the layer configuration further comprises at least one photovoltaic layer. The photovoltaic layer may be organic layer, a hybrid inorganic and organic layer or an inorganic layer.
According to a twenty-eighth embodiment of the layer configuration, according to the present invention, the layer configuration is a solar cell. Photovoltaic devices incorporating the layer configuration, according to the present invention, can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode. In the case of the regenerative type of photovoltaic cell, as exemplified by the Graetzel cell, the hole transporting medium may be a liquid electrolyte supporting a redox reaction, a gel electrolyte supporting a redox reaction, an organic hole transporting material, which may be a low molecular weight material such as 2, 2 ' , 7, 7 ' -tetrakis (N, N-di-p-methoxyphenyl- amine) 9, 9' -spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, poly (N-vinylcarbazole) etc., or inorganic semiconductors such as Cul, CuSCN etc. The charge transporting process can be ionic as in the case of a liquid electrolyte or gel electrolyte or electronic as in the case of organic or inorganic hole transporting materials.
Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types : structures which receive light from both sides and those which receive light from one side. An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer. Such devices preferably have their sides sealed with a polymer, an adhesive or other means to prevent deterioration or volatilization of the inside substances. The external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known.
Organic photovoltaic layers of the layer configuration, according to the present invention are, for example, mixtures of fullerene molecules (as electron acceptor and electron transporter) with conjugated polymers (e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter) [see Brabec et al . , Adv. Funct. Mater., volume 11(1), pages 15 - 26 (2001)]. In 1995 Halls et al . reported in Nature, volume 376, page 498 the successful use of acceptor-type conjugated polymers instead of fullerenes . Alternatively the layer configuration, according to the present invention, can be incorporated in hybrid photovoltaic compositions such as described in 1991 by Graetzel et al . in Nature, volume 353, pages 737-740, in 1998 by U. Bach et al . [see Nature, volume 395, pages 583-585 (1998)] and in 2002 by W. U. Huynh et al . [see Science, volume 295, pages 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transporter or hole transporter) is inorganic (e.g. nano- Tiθ2 as electron transporter, CdSe as light absorber and electron transporter) and at least one of the components is organic (e.g. triphenylamine as hole transporter or poly (3-hexylthiophene) as hole transporter) .
Inorganic photovoltaic layers which can be used in the layer configuration according to this invention are described in EP-A 1 176 646.
Transistors
According to a twenty-ninth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer with one or more of the electron transporting or hole transporting components described above, but within such a configuration that it can be used as a transistor. The semiconductor can be n-type, p-type or both (ambipolar transistor) and can be either organic or inorganic.
Industrial application
Layer configurations comprising an element, according to the present invention, between a positive electrode and a material capable of hole transport and capable of reducing hole-electron recombination at the positive electrode can be used in a wide range of electronic devices such as photovoltaic devices, solar cells, batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, sensors for organic and bio-organic materials and field effect transistors [see also chapter 10 of the Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, Weinheim (1999)].
The invention is illustrated hereinafter by way of reference light emitting devices and light emitting devices according to the present invention. The percentages and ratios given in these examples are by weight unless otherwise indicated.
Ingredients used in the element between the patterned ITO-electrode and the electroluminescent layer of reference light emitting devices :
Celquat™ SC240C a cationic p-saccharide from National Starch and Chemical
Celquat™ L200 a cationic cellulose from National Starch and Chemical
LIGHT EMITTING DEVICES 1 to 9
Preparation of the Electroluminescent ZnS:Cu dispersion
The following solutions were prepared:
Figure imgf000019_0001
*TRI = (5-methyl-l , 2, 4-triazolo- (1, 5-a) -pyrimidine-7-ol)
Solutions 1 and 2 at room temperature were added simultaneously both at a flow rate of 500 mL/min to solution 3, held at room temperature and stirred at 1500 rpm for 60 s. To 1000 mL of the resulting dispersion, 1000 mL of a 1% polyphosphoric acid solution adjusted to pH 6 with ammonium hydroxide was added and the dispersion was concentrated to 1000 mL by means ultrafiltration using a Fresenius F60 cartridge. This dispersion was subsequently diafiltered by using 5500 mL of a 1% solution of polyphosphoric acid solution adjusted to pH 6 with ammonium hydroxide solution in water. The dispersion was further concentrated to a volume of about 570 mL to produce an aqueous dispersion at pH 6 containing 30g/L ZnS:Cu and 1% polyphosphoric acid. The dispersion was then ball- milled for 1 hour. 20 mL of the resulting dispersion was then ultrasonically treated with a ultrasound bar (Vibra cell VCX 400 W from Sonics & Materials Inc. - amplitude about 78% - output 40%) for 3 minutes while cooling in ice. 3.2 g of a 5% by weight aqueous solution of poly (vinylpyrrolidone) in water was then added to 16.8 g of the ZnS:Cu dispersion followed by further ultrasonic treatment with the ultrasound bar for 5 minutes. 0.5 mL of ZONYL™ FSO100 was then added as a 1% by weight aqueous solution followed by thorough stirring. The resulting dispersion was then filtered through a 5 μm MILLIPORE™ filter, a nano-dispersion of electroluminescent ZnS:Cu being thereby produced.
Preparation of the patterned ITO electrode
An indium tin oxide [ITO] layer on 175 μm thick poly (ethylene terephthalate) [PET] from 1ST, with a surface resistance of about
80 Ohm/square, was used as the hole-conducting electrode. ITO/PET
2 sheets of 5 x 5 cm were taped off in the middle of the plate with a 2 cm Magic tape Scotch 810 from 3M. The sides of the ITO plates were etched with a solution consisting of 50 mL of concentrated hydrochloric acid, 50 mL of deionized water and 4 mL of concentrated nitric acid. After the etching, the ITO/PET sheets were rinsed with water several times and subsequently dried with a hair dryer. After drying, the tape was removed and the sheets were put into a vessel with iso-propanol which was put into an ultrasound bath for 10 minutes. Afterwards they were dried at 50°C for 10 minutes. Each ITO/PET sheet contained a band of 2 cm of conductive ITO in the middle. Preparation and application of the element between the patterned ITO electrode and the electroluminescent layer
5 The solutions/dispersions were prepared by stirring the ingredients in Table 1 together in the quantities given therein and then adjusting the pH or not as indicated therein.
Solutions 4, 6, 8 and 10 were spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s. This resulted in 10 an element thickness of about 5 to 10 nm. The substrates for devices 2, 4, 6 and 8 were thereby produced.
Solutions 5, 7, 9 and 11 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s. This resulted in an element thickness of about 100 nm thereby producing 75 the substrates for devices 3, 5, 7 and 9 respectively.
The thicknesses were measured with a DEKTAK™ profilometer with the element spincoated on glass. Similar element thicknesses can be expected on ITO/PET.
20 Table 1:
Figure imgf000021_0001
Application of the electroluminescent layer
25 The electroluminescent nano ZnS : Cu-dispersion was spincoated at 1000 rpm for 6 s and then at 2000 rpm for 50 s on the substrates of devices 1 to 9, device 1 without an elctron blocking element and devices 2 to 9 with the above-described electron blocking elements. The resulting electroluminescent ZnS : Cu-layers were then dried at
30 50°C for 10 minutes, a thickness of lOOnm being thereby obtained.
Application of the aluminium electrode Subsequently, a 160 nm thick aluminium electrode (cathode) was vacuum deposited on the spincoated double layers at a vacuum of
-4 -2 . 2
1.33 x 10 N m Pa using a mask. The emission area was 25 mm . The device construction is shown in Figure 1.
Performance of the light emitting devices
The results of the light emitting devices produced without the additional layer between the patterned ITO-electrode and the ZnS:Cu luminescent layer, light emitting device 1, and with the different layers, light emitting devices 1 to 9, are given in Table 2.
It should be noted that the lifetime of these light emitting devices was found to be dependent upon the relative humidity pertaining at the time the devices were produced, decreasing with increasing ambient relative humidity. The lifetimes of reference devices without the additional element between the patterned ITO- electrode and the ZnS:Cu luminescent layer varied between 25 and 793 s during the research resulting in the present invention. Therefore, results from series of devices produced on different days can only be directly compared with one another, if the performances of the reference devices without the additional element between the patterned ITO-electrode and the ZnS:Cu luminescent layer were comparable. At a forward bias, the devices exhibited electroluminescence with a λmax of 490 nm. For the lifetime measurements, a forward bias was applied and the voltage was increased so as to keep the
2 light output constant at ca. 0.5 Cd/m . The maximum voltage was 12
V. The lifetime of the light emitting device was taken to be the time between the application of the optimum voltage and the moment no further electroluminescence could be observed. The optimum voltage was that voltage at which maximum light output was observed. Table 2
Figure imgf000023_0001
It can be concluded from Table 2 that the presence of an element containing a polycarboxy-polymer between the hole conductor (ITO) and the electroluminescent layer improves the lifetime of the devices. This can probably be explained by preventing electrons reaching the ITO layer. Indeed it was found that the (surface) resistance of the ITO after the lifetime experiments had substantially increased to greater than 1000 ohm/square, indicating that recombination of electrons and holes had taken place in the ITO layer. Furthermore, no significant difference in lifetime was found between 5 nm and 100 nm elements of polycarboxy-polymers.
LIGHT EMITTING DEVICES 10 to 16
Devices 10 to 16 were prepared as described for Devices 1 to 9 except that the patterned ITO electrode was coated with elements incorporating PAP-01. Solutions 12 to 17, used for preparing these elements, prepared as described for Solutions 1 to 11, are given below in Table 3.
Table 3:
Figure imgf000023_0002
17 I - 1 - j - 1 0 . 3 1 1 1 48 .7 1 HBr [ 2 . 5
Solutions 12 and 13 were spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 1500 rpm for 50 s and the element dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm, thereby producing the substrates for device 11 and 12 respectively.
Solutions 14, 15, 16 and 17 were spincoated on a patterned ITO/PET sheet at 800 rpm for 6 s and then at 4000 rpm for 50 s and the element dried at 40 °C for 10 minutes. This resulted in element thicknesses of about 5 to 10 nm, thereby producing the substrates for devices 13, 14, 15 and 16 respectively.
Performance of the light emitting devices
The results for light emitting devices 10 to 16, obtained as for light emitting devices 1 to 9, are given in Table 4.
It can be concluded from Table 4 that the presence of an element containing a polyamine-polymer quaternized with HC1 between the hole conductor (ITO) and the electroluminescent layer improves the lifetime of the devices with increasing element thickness in the cases of devices with elements of PAP-01 and PAP-02 for which at a thickness of 100 nm an improvement in lifetime over the reference device, device 10.
In the cases of devices with elements of PAP-03 and PAP-04, the performance of the devices is dependent upon the acid used to at least partially quaternize the polyamine-polymers. For PAP-03 there was an improvement for 5 nm elements in the case of quaternization with p-toluenesulphonic acid and hydrobromic acid. For PAP-04 there was an improvement for 5 nm elements in the case of quaternization with p-toluenesulphonic acid and hydrochloric acid. Table 4
Figure imgf000025_0001
LIGHT EMITTING DEVICES 17 to 19
Devices 18 and 19 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating poly (vinyl phosphonic acid) . Solutions 18 and 19, used for preparing these elements, prepared as described for Solutions 4 to 11, are given below in Table 5.
Table 5:
Figure imgf000025_0002
Solution 18 was spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in an element thickness of about 5 to 10 nm, thereby producing the substrate for device 18.
Solution 19 was spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in an element thickness of about 100 nm, thereby producing the substrate for device 19.
Performance of the light emitting devices
The results for light emitting devices 18 and 19 obtained as for light emitting devices 1 to 9, are given in Table 6 together with the results of reference light emitting device 17 coated with the same batch of ZnS:Cu dispersion in the same series of coatings as devices 18 and 19. Table 6
Figure imgf000026_0001
It can be concluded from Table 6 that the presence of an element of poly (vinylphosphonic acid) between the hole conductor (ITO) and the electroluminescent layer improves the lifetime of the devices for both thicknesses of 5 nm and 100 nm. This can probably be explained by preventing electrons reaching the ITO layer. Indeed it was found that the (surface) resistance of the ITO after the lifetime experiments had substantially increased to greater than 1000 ohm/square, indicating that recombination of electrons and holes had taken place in the ITO layer.
Furthermore, devices with 5 nm and 100 nm poly (vinylphosphonic acid) elements exhibited a decrease in lifetime between element thicknesses of 5 nm and 100 nm.
LIGHT EMITTING DEVICES 20 to 22
Devices 20 to 22 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating polyacrylamide . Solutions 20 and 21, used for preparing these elements, prepared as described for Solutions 4 to 11, are given below in Table 7.
Table 7
Figure imgf000026_0002
Solution 20 was spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40 °C for 10 minutes. This resulted in an element thickness of about 5 to 10 nm, thereby producing the substrate for device 21.
Solution 21 was spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40 °C for 10 minutes. This resulted in an element thickness of about 100 nm, thereby producing the substrate for device 22. Performance of the light emitting devices
The results for light emitting devices 21 and 22 obtained as for light emitting devices 1 to 9, are given in Table 8 together with the results of the reference light emitting device 20 coated with the same batch of ZnS:Cu dispersion in the same series of coatings as devices 21 and 22.
Table 8 :
Figure imgf000027_0001
It can be concluded from Table 8 that the presence of an element of polyacrylamide between the hole conductor (ITO) and the electroluminescent layer worsened the lifetime of the devices for both thicknesses of 5 nm and 100 nm. This shows that not all polymer elements incorporated between the patterned ITO-electrode and the ZnS:Cu electroluminescent layer exhibit a beneficial effect on the lifetime of such devices .
LIGHT EMITTING DEVICES 23 to 26
Devices 23 to 26 were prepared as described for Devices 2 to 9 except that the patterned ITO electrode was coated with elements incorporating polyacrylamide. Solutions 22 to 25, used for preparing these elements, prepared as described for Solutions 1 to 11, are given below in Table 9.
Table 9:
Figure imgf000027_0002
Solutions 22 and 24 were spincoated on patterned ITO/PET at
800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40 °C for 10 minutes. This resulted in element thicknesses of about 5 to 10 nm, thereby producing the substrates for devices 23 and 25 respectively.
Solutions 23 and 25 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm, thereby producing the substrates for devices 24 and 26 respectively.
Performance of the light emitting devices
The results for light emitting devices 23 to 26, obtained as for light emitting devices 1 to 9, are given in Table 10 together with the results of reference light emitting device 10, which was coated with the same batch of ZnS:Cu dispersion in the same series of coatings as devices 23 to 26.
Table 10:
Figure imgf000028_0001
It can be concluded from Table 10 that the presence of an element of Celquat™ SC240C and Celquat™ L200, a cationic p-saccharide and a cationic cellulose respectively, between the hole conductor (ITO) and the electroluminescent layer worsened the lifetime of the devices for both thicknesses of 5 nm and 100 nm. This shows that not all polymer elements incorporated between the patterned ITO- electrode and the ZnS:Cu electroluminescent layer exhibit a beneficial effect on the lifetime of such devices.
The present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

Claims

1. A layer configuration on a support, said layer configuration comprising a non-photoactive element exclusive of poly (3,4- alkylenedioxythiophene) s, said element containing at least one polymer selected from the group consisting of polycarboxy- polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) , the surface of one side of said element being contiguous with a positive electrode and the surface on the opposite side of said element being contiguous with a material capable of transporting holes .
2. Layer configuration according to claim 1, wherein said polycarboxy-polymer is a polymer containing optionally substituted acrylic acid monomer units .
3. Layer configuration according to claim 2, wherein said optionally substituted acrylic acid monomer units are selected from the group consisting of: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid and citraconic acid.
4. Layer configuration according to claim 1 or 2, wherein said polycarboxy-polymer is polyacrylic acid or polymethacrylic acid.
5. Layer configuration according to claim 1, wherein said optionally quaternized aliphatic polyamine-polymer is polyallylamine hydrochloride, an optionally quaternized polyvinylpyridine or a copolymer of an optionally quaternized vinyl pyridine .
6. A light emitting diode consisting of a layer configuration on a support, said layer configuration comprising a non- photoactive element exclusive of poly (3,4- alkylenedioxythiophene) s, said element containing at least one polymer selected from the group consisting of polycarboxy- polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid) , the surface of one side of said element being contiguous with a positive electrode and the surface on the opposite side of said element being contiguous with a material capable of transporting holes .
7. A photovoltaic device consisting of a layer configuration on a support, said layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxythiophene) s, said element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of said element being contiguous with a positive electrode and the surface on the opposite side of said element being contiguous with a material capable of transporting holes.
8. A transistor consisting of a layer configuration on a support, said layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxythiophene) s, said element containing at least one polymer selected from the group consisting of polycarboxy-polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of said element being contiguous with a positive electrode and the surface on the opposite side of said element being contiguous with a material capable of transporting holes .
9. An electroluminescent device consisting of a layer configuration on a support, said layer configuration comprising a non-photoactive element exclusive of poly (3, 4- alkylenedioxythiophene) s, said element containing at least one polymer selected from the group consisting of polycarboxy- polymers, optionally quaternized polyamine-polymers and poly (vinylphosphonic acid), the surface of one side of said element being contiguous with a positive electrode and the surface on the opposite side of said element being contiguous with a material capable of transporting holes.
PCT/EP2003/050344 2002-08-23 2003-07-29 Layer configuration comprising an electron-blocking element WO2004019348A1 (en)

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