EP1532640A1 - Procede pour preparer une couche conductrice sensiblement transparente - Google Patents

Procede pour preparer une couche conductrice sensiblement transparente

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Publication number
EP1532640A1
EP1532640A1 EP02807724A EP02807724A EP1532640A1 EP 1532640 A1 EP1532640 A1 EP 1532640A1 EP 02807724 A EP02807724 A EP 02807724A EP 02807724 A EP02807724 A EP 02807724A EP 1532640 A1 EP1532640 A1 EP 1532640A1
Authority
EP
European Patent Office
Prior art keywords
layer
conductive
group
uniformly distributed
intrinsically
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP02807724A
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German (de)
English (en)
Inventor
Hieronymus AGFA-GEVAERT ANDRIESSEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Publication of EP1532640A1 publication Critical patent/EP1532640A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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 single layer composite substantially transparent conductive layer .
  • Highly conductive (non- transparent) patterns can be made by screen-printing conducting pastes such as silver or carbon black pastes .
  • Vacuum evaporation of metals through shadow masks is another method .
  • Yet another method makes use of homogeneous conductive metallized surfaces which can be patterned by use of photoresist technology in combination with a metal etching agent .
  • Photographic f ilms can, under certain conditions , be used for making electrically conductive silver "images " .
  • US 3,664,837 describes the use of light sensitive evaporated silver halide film which upon exposure and after development results in conductive images.
  • DE 1,938,373 describes a photographic method for producing conducting paths, resistances and capacitors for microcircuits starting from coated silver halide emulsions.
  • US 3,600,185 describes the production of electrically conductive patterns by means of diffusion transfer techniques.
  • DE-A 196 27 071 discloses an electroluminescent configuration, which contains hole and/or electron injecting layers, wherein the polymeric organic conductor is selected from the group of polyfurans, polypyrroles, polyanilines, polythiophenes and polypyridines .
  • DE-A 196 27 071 also discloses the use of poly (3 , 4-ethylenedioxythiophene) as a charge-in ection layer on transparent metallic electrodes such as ITO (indium-tin oxide) and that the following materials are suitable as transparent and conductive materials: a) metal oxides e.g. ITO, tin oxide etc.; b) semi-transparent metal films e.g. Au, Pt, Ag, Cu etc. The latter being applied by vacuum techniques.
  • EP-A 510 541 discloses an organic electroluminescent device having an anode, an organic hole injection transport layer, an organic luminescent layer and a cathode formed sequentially in this order, wherein the organic hole injection transport layer contains a metal complex and/or a metal salt of an aromatic carboxylic acid.
  • EP-A 510 541 further discloses that the conductive layers used in such devices may have a multi-layer structure by depositing different types of conductive materials selected from a metal, e.g. Al , Au, Ag, Ni, Pd or Te, a metal oxide, carbon black or a conductive resin such as poly (3-methylthiophene) , but no specific combinations are exemplified.
  • US 5,447,824 discloses a method of manufacturing a pattern of an electrically conductive polymer on a substrate surface, said method comprising: a) forming a liquid layer on a surface of said substrate from a solution containing a material capable of forming said electrically conductive polymer upon being heated, e.g. 3,4- ethylenedioxythiophene, an oxidizing agent and a base, b) exposing said liquid layer to patterned radiation, and c) heating said layer thereby forming a pattern of an electrically conductive polymer, said conductive polymer being formed in unexposed areas and a non- conductive polymer being formed in the exposed areas of the layer.
  • a metal layer e.g. silver, copper, nickel or chromium
  • WO 98/54767 discloses a conductive layer system, particularly for a transparent or semi-transparent electrode or electroluminescent configuration, comprising at least two layers, characterized in that the first layer contains an organic or organometallic electrically conductive polymer, which is transparent or semi-transparent in the visible range of the electromagnetic spectrum, e.g. a polymer selected from the group consisting of polythiophene, polypyrrole, polyaniline, polyacetylene or their optionally substituted derivatives and the second layer contains at least one electrically conductive inorganic compound or a metal or an appropriately doped semi-metal e.g.
  • invention example 2 discloses a poly (3 , 4-ethylenedioxythiophene) [PEDOT] /poly (styrene sulphonate) [PSS] layer with a surface resistivity of 1500 ⁇ /square to which conducting tracks of "Leitsilber” (a silver particle dispersion) ca. 2 mm wide had been applied by a printing technique.
  • the layer configuration disclosed in Example 2 of WO 98/54767 has the disadvantages of the grid of "Leitsilber” requiring a thickness of 5 to 10 ⁇ m to realize layers with a surface resistance of 0.5 to 1 ⁇ /square, which means that the surface of the configuration will have a certain roughness which will limit its applications, making it difficult to apply a thin, e.g. 100 nm, functional layer. Furthermore, an aqueous PEDOT/PSS dispersion would not wet such a "Leitsilber” grid and hence a usable multilayer conductive configuration would not result. Moreover, with an intrinsically conductive polymer layer or a metal grid outermost wetting problems arise as regards coating of thin functional layers. Furthermore, for devices requiring very thin functional layers such as transistors, the thickness of a multilayer electrode and even slight deviations from flatness are disadvantageous in their production.
  • a thin substantially transparent conductive layer with high conductivity and with an outermost surface with improved flatness can be realized in a layer containing an intrinsically conductive polymer, e.g. PEDOT/PSS, and a conductive metal, e.g. silver, non-uniformly distributed therein to which functional layers can be readily applied.
  • an intrinsically conductive polymer e.g. PEDOT/PSS
  • a conductive metal e.g. silver
  • aspects of the present invention are also realized by a process for preparing a substantially transparent conductive layer on a support, the layer comprising an intrinsically conductive polymer and a conductive metal non-uniformly distributed therein and forming of itself a conductive entity, comprising the step of: preparing the non-uniformly distributed conductive metal by a photographic process.
  • Figure 1 shows four silver patterns, pattern (a) representing a continuous silver layer 3 x 3 cm 2 in area, pattern (b) representing a regular strip pattern, the parallel strips being 10 mm apart and having a width of 1 mm; pattern (c) representing a regular strip pattern, the parallel strips being 5 mm apart and having a width of 150 ⁇ ; and pattern (d) representing no silver development.
  • 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. methanol, ethanol,
  • support means a "self-supporting material” so as to distinguish it from a "layer” which may be coated on a support, but which is itself not self-supporting. It also includes any treatment necessary for, or layer applied to aid, adhesion to the support .
  • continuous layer refers to a layer in a single plane covering the whole area of the support and not necessarily in direct contact with the support.
  • non-continuous layer refers to a layer in a single plane not covering the whole area of the support and not necessarily in direct contact with the support.
  • coating in used as a generic term including all means of applying a layer including all techniques for producing continuous layers, such as curtain coating and doctor-blade coating and all techniques for producing non-continuous layers such as screen printing, ink jet printing, flexographic printing, and techniques for producing continuous layers
  • intrinsically conductive polymer means organic polymers which have (poly) -conjugated ⁇ -electron systems (e.g. double bonds, aromatic or heteroaromatic rings or triple bonds) and whose conductive properties are not influenced by environmental factors such as relative humidity.
  • the term "conductive" is related to the electric resistance of the material.
  • the electric resistance of a layer is generally expressed in terms of surface resistance R s (often specified as ⁇ /square) .
  • photographic refers to any photochemical process particularly those based on silver halide processes.
  • silver salt diffusion transfer process refers to a process developed independently by A. Rott [GB 614,155 and Sci. Photogr., (2)13, 151 (1942)]and E. Weyde [DE 973,769] and described by G. I. P. Levenson in Chapter 16 of "The Theory of the Photographic Process Fourth Edition", edited by T. H. James, pages 466 to 480, Eastman Kodak Company, Rochester (1977).
  • substantially transparent means that the integral transmission of visible light is above 50% of the incident light normal to the conductive layer of the present invention i.e. the layer had an overall • optical density of less than 0.30, although local transmission of visible light though the lines of the silver pattern may be well below 10% of the incident light normal to the conductive layer of the present invention i.e. well above an optical density of 1.0.
  • PEDOT poly (3 , 4-ethylenedioxy- thiophene) .
  • PSS poly(styrene sulphonic acid) or poly (styrenesulphonate) .
  • a substantially transparent conductive layer on a support comprising an intrinsically conductive polymer and a conductive metal non-uniformly distributed therein and forming of itself a conductive entity.
  • the conductive metal is silver.
  • the intrinsically conductive polymers used in the present invention can be any intrinsically conductive polymer known in the art e.g. polyacetylene, polypyrrole, polyaniline, polythiophene, etc. Details about suitable intrinsically conductive polymers can be found in textbooks, such as "Advances in Synthetic Metals", ed. P. Bernier, S. Levers, and G. Bidan, Elsevier, 1999; “Intrinsically Conducting Polymers: An Emerging Technology", Kluwer (1993); “Conducting Polymer Fundamentals and Applications, A Practical Approach", P. Chandrasekhar, Kluwer, 1999; and “Handbook of Organic Conducting Molecules and Polymers", Ed. Walwa, Vol. 1-4, Marcel Dekker Inc. (1997) .
  • the intrinsically conductive polymer contains structural units represented by formula (I):
  • each of R and R ⁇ independently represents hydrogen or _ C ⁇ - 4 alkyl group or together represent an optionally substituted C ⁇ - 4 alkylene group or a cycloalkylene group.
  • the intrinsically conductive polymer is a polymer or copolymer of a 3 , 4-dialkoxythiophene in which the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge.
  • the intrinsically conductive polymer is a polymer or copolymer of a 3 , 4-dialkoxy-thiophenes in which the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge and is selected from the group consisting of: poly (3 , 4-methylenedioxythiophene) , poly(3,4- methylenedioxythiophene) derivatives, poly(3 , 4-ethylenedioxy- thiophene) , poly(3 , 4-ethylenedioxythiophene) derivatives, poly(3,4- propylenedioxythiophene) , poly (3 , 4-propylenedioxythiophene) derivatives, poly (3 , 4-butylenedioxythiophene) and poly (3, 4- butylenedioxythiophene) derivatives and copolymers thereof.
  • the intrinsically conductive polymer is a polymer or copolymer of a 3 , 4-dialkoxy-thiophenes in which the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge and the substituents for the oxy-alkylene-oxy bridge are alkyl, alkoxy, alkyloxyalkyl, carboxy, alkylsulfonato and carboxy ester groups.
  • the intrinsically conductive polymer is a polymer or copolymer of a 3 , 4-dialkoxy-thiophenes in which the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge and the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge which is a 1,2-ethylene group, an optionally alkyl- substituted methylene group, an optionally C ⁇ - 12 -alkyl- or phenyl- substituted 1,2-ethylene group, a 1, 3-propylene group or a 1,2- cyclohexylene group.
  • Such polymers are disclosed in Handbook of Oligo- and
  • Organic polymer containing structural units according to formula (I) can be polymerized chemically or electrochemically. Chemical polymerization can be carried out oxidatively or reductively.
  • the oxidation agents used for the oxidative polymerisation of pyrrole such as described for example in J. Amer. Chem. Soc . , vol. 85, pages 454-458 (1963) and J. Polym. Sci. Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988), can be utilized for the oxidative polymerization of thiophenes.
  • the inexpensive and easily accessible oxidation agents such as iron (III) salts such as FeCl 3 , the iron(III) salts of organic acids, e.g. Fe(OTs) 3 , H 2 0 2 , K 2 Cr 2 ⁇ 7 , alkali and ammonium persulphates, alkali perborates and potassium permanganate are used in the oxidative polymerization.
  • oxidative polymerization of thiophenes requires 2.25 equivalents of oxidation agent per mole thiophene of formula (I) [see e.g. J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988)]. In practice an excess of 0.1 to 2 equivalents of oxidation agent is used per polymerizable unit. The use of persulphates and iron (III) salts has the great technical advantage that they do not act corrosively. Furthermore, in the presence of particular additives oxidative polymerization of the thiophene compounds according to formula (I) proceeds so slowly that the thiophenes and oxidation agent can be brought together as a solution or paste and applied to the substrate to be treated. After application of such solutions or pastes the oxidative polymerization can be accelerated by heating the coated substrate as disclosed in US 6,001,281 and WO 00/14139 herein incorporated by reference.
  • Reductive polymerization can be performed using the Stille (organotin) or Suzuki (organoboron) routes described in 2002 by Appperloo et al. in Chem. Eur. Journal, volume 8, pages 2384-2396, and as disclosed in 2001 in Tetrahedron Letters, volume 42, pages 155-157 and in 1998 in Macromolecules, volume 31, pages 2047-2056 respectively or with nickel complexes as disclosed in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621 and in 1998 in Advanced Materials, volume 10, pages 93-116.
  • the conductive layer further contains a silver-ion stabilizer.
  • the conductive layer further contains a silver-ion stabilizer which is a 1-phenyl-5-mercato- tetrazole compound in which the phenyl group is substituted with one or more electron accepting groups.
  • the conductive layer further contains a silver-ion stabilizer which is a l-phenyl-5-mercato- tetrazole compound in which the phenyl group is substituted with one or more electron accepting groups groups selected from the group consisting of chloride, fluoride, cyano, sulfonyl, nitro, acid amido and acylamino groups.
  • a silver-ion stabilizer which is a l-phenyl-5-mercato- tetrazole compound in which the phenyl group is substituted with one or more electron accepting groups groups selected from the group consisting of chloride, fluoride, cyano, sulfonyl, nitro, acid amido and acylamino groups.
  • the conductive layer further contains a silver-ion stabilizer which is selected from the group consisting of: 1- (3 ' , 4' -dichlorophenyl) -5-mercapto-tetrazole,
  • Suitable l-phenyl-5-mercapto-tetrazole compounds with substituted phenyl groups [PMT] include:
  • aspects of the present invention are also realized by a process for preparing a substantially transparent conductive layer on a support, the layer comprising an intrinsically conductive polymer and a conductive metal non-uniformly distributed therein and forming of itself a conductive entity, comprising the step of: preparing the non-uniformly distributed conductive metal by a photographic process.
  • the photographic process comprises the steps of: coating the support with a layer containing the intrinsically conductive polymer and a nucleation agent; producing a non- continuous silver layer in the nucleation layer using silver salt diffusion transfer.
  • the photographic process comprises the steps of: coating the support with a layer containing the intrinsically conductive polymer and palladium sulphide e.g. palladium sulphide nanoparticles, as a nucleation agent; producing a non-continuous silver layer in the nucleation layer using silver salt diffusion transfer.
  • a layer containing the intrinsically conductive polymer and palladium sulphide e.g. palladium sulphide nanoparticles as a nucleation agent
  • the photographic process comprises the steps of: coating the support with a layer containing an intrinsically conductive polymer, silver halide and gelatin with a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3, image-wise exposing the layer, and developing the exposed layer to produce the non-uniformly distributed silver.
  • the conductive layer further contains a surfactant.
  • the conductive layer 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
  • the conductive layer 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. 17 ZONYLTM UR: [F(CF 2 CF 2 ) ⁇ - 7 CH CH 2 0] 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 conductive layer further contains a binder.
  • the conductive layer further contains a cross-linking agent.
  • the support is transparent or translucent .
  • the support is a polymeric film, silicon, a ceramic, an oxide, glass, polymeric film reinforced glass, a glass/plastic laminate, a metal/plastic laminate, optionally treated paper and laminated paper.
  • the support is provided with a subbing layer or other adhesion promoting means to aid adhesion to the substantially transparent conductive layer.
  • 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) , poly (ethylene naphthalene-1 , 4-dicarboxylate) , polystyrene, polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides, cellulosetriacetate, polyolefins and poly(vinylchloride) , optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • poly (ethylene terephthalate) poly (ethylene naphthalene-1 , 4-dicarboxylate)
  • polystyrene polyethersulphone
  • polycarbonate polyacrylate
  • polyamide polyimides
  • cellulosetriacetate polyolefins
  • poly(vinylchloride) optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • an electroluminescent device comprising the conductive layer, according to the present invention, or produced according to the process, according to the present invention.
  • 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 ologomers (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 e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer e.g. In
  • 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.
  • 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 (Alq 3 ) , polyaromatics (anthracene derivatives, perylene derivatives and stilbene derivatives) and polyhetero-aromatics (oxazoles, oxadiazoles, thiazoles etc.) can be used as electroluminescent compounds .
  • 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) , poly (p-phenylene ethynylenes) etc .
  • PVK non-conjugated polyvinylcarbazole derivatives
  • conjugated polymers like poly (p-phenylene vinylenes) (PPV) , polyfluorenes , poly (3-alkylthiophene) , poly (p-phenylene ethynylenes) etc .
  • 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.
  • an aluminium electrode is applied by evaporation.
  • ITO positive a direct current voltage of several volts
  • 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.
  • high electric fields occur and electroluminescence is already possible at low voltages (typically between 10 and 30 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)], herein incorporated by reference.
  • the electroluminescent device is a light emitting diode.
  • the electroluminescent device further comprises a layer of an electroluminescent phosphor.
  • the electroluminescent device comprises a layer of an electroluminescent 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 and all the rare earths e.g. Cu, Ag, Mn, Eu, Sm, Tb and Ce.
  • the electroluminescent device comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is encapsulated with a transparent barrier layer against moisture e.g. AI 2 O 3 and AlN.
  • a transparent barrier layer against moisture e.g. AI 2 O 3 and AlN.
  • Such phosphors are available from Sylvania, Shinetsu polymer KK, Durel, Acheson and Toshiba.
  • An example of coatings with such phosphors is 72X, available from Sylvania/GT ⁇ , and coatings disclosed in US 4,855,189.
  • the electroluminescent device further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with manganese, copper or terbium, or CaGa 2 S 4 doped with cerium e.g. the electroluminescent phosphor pastes supplied by DuPont: LUXPRINTTM type 7138J, a white phosphor; LUXPRINTTM type 7151J, a green-blue phosphor; and LUXPRINTTM type 7174J, a yellow-green phosphor; and ELECTRODAGTM EL-035A supplied by Acheson.
  • the electroluminescent phosphor pastes supplied by DuPont LUXPRINTTM type 7138J, a white phosphor; LUXPRINTTM type 7151J, a green-blue phosphor; and LUXPRINTTM type 7174J, a yellow-green phosphor; and ELECTRODAGTM EL-035A supplied
  • the electroluminescent device further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is a zinc sulphide phosphor doped with manganese and encapsulated with AlN.
  • the electroluminescent device 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 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. Aspects of the present invention are also realized by a light emitting diode comprising the above-described conductive layer or produced according to the above-described process.
  • the light-emitting diode further comprises a electroluminescent layer comprising a low molecular weight electroluminescent compound.
  • the light-emitting diode further comprises a electroluminescent layer comprising a polymeric electroluminescent compound.
  • the light-emitting diode further comprises electroluminescent quantum dots.
  • aspects of the present invention are also realized by a photovoltaic device comprising the conductive layer, according to the present invention, or produced according to the process, according to the present invention.
  • aspects of the present invention are also realized by a solar cell comprising the conductive layer, according to the present invention, or produced according to the process, according to the present invention.
  • the photovoltaic device further comprises at least one photovoltaic layer.
  • the photovoltaic layer may be organic layer, a hybrid inorganic and organic layer or an inorganic layer.
  • Photovoltaic devices incorporating the conductive layer 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 electron transporting medium may be a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV, such as titanium dioxide, niobium(V) oxide, tantalum(V) oxide and zinc oxide
  • 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 C
  • 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.
  • the spectrally sensitized nano-porous metal oxide 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-Ti ⁇ 2 as electron transporter CdSe as light absorber and electron transporter
  • at least one of the components is organic (e.g. triphenylamine as hole transporter or poly (3-hexylthiophene) as hole transporter) .
  • the transistor 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 .
  • a conductive layer 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 INVENTION and COMPARATIVE EXAMPLES . The percentages and ratios given in these examples are by weight unless otherwise indicated.
  • PdS physical development nuclei
  • Al a 10 g/L water solution of Aerosol OT from American Cyanamid
  • 5 g of a 50 g/L solution of perfluorcaprylamide-polyglycol were added.
  • This dispersion was then coated to a wet layer thickness of 13.5 ⁇ m on a poly (ethylene terephthalate) support with a 4 ⁇ m thick gelatine subbing layer and then dried for 60 minutes at 25°C. This is material A.
  • EP-A 686662 and US 5,766,515 disclose in the example the preparation of a 1.2% PEDOT/PSS dispersion in water. 15 ml of a 2% solution of ZONYLTM FSO100 in water, 1.25 g of Z6040, a silane from DOW CORNING and 25 g of diethylene glycol were added to 106 g of this dispersion to give the PEDOT/PSS dispersion used in the following EXAMPLES.
  • the above-described PEDOT/PSS dispersion was used to coat Material A to a wet thickness of 40 ⁇ m and was then dried for 15 minutes at 100°C, thereby producing material C.
  • the transfer emulsion layer was exposed image-wise as shown in Figure 1 and processed in contact with the receiver (Material A and material B) at 25°C for 10s with a AGFA-GEVAERTTM CP297 developer solution.
  • Processed material A was coated with the above-described
  • PEDOT/PSS-dispersion to a wet-layer thickness of 50 ⁇ m and then dried for 20 minutes at 120°C.
  • the surface resistivity of the PEDOT/PSS layer was about 500 ⁇ /square in the non-exposed areas of material A. Material C was thereby prepared.
  • the surface resistance measurements were carried out as follows: the layer electrode configurations were cut into strips 3.5 cm in width to ensure perfect positioning of the electrode material; parallel copper electrodes each 35 mm long, 3 mm wide and 35 mm apart, capable of forming line contacts and mounted on a TEFLONTM insulator were brought into contact with the outermost conductive layer of the strip giving a contacting area of 3.5 x 3.5
  • the optical density of the conductive layers was determined in transmission using a MacBethTM TD924 densitometer with a visible filter for conductive layers without photographic treatment, in pattern type (d) in which no silver was developed and in pattern (a) in which silver was developed over the whole 3 cm x 3 cm area without deducting the density of the support.
  • the surface resistances and optical densities (complete material) after exposure and development according to the patterns shown in Figure 1 are given in Table 1. Table 1 :
  • PdS physical development nuclei
  • the preparation of the silver chlorobromide emulsion and the preparation of the transfer emulsion layer was as disclosed in EP-A 769 723 except that the coverage of silver halide applied was equivalent to 1.25 g/m 2 of AgN0 3 instead of 2 g/m2 thereof.
  • the transfer emulsion layer was exposed image-wise as shown in
  • Electrodes were conditioned for 3 days at 35°C and a relative humidity of 80%.
  • the aqueous solutions used for treating the electrodes prior to applying a potential of 100 V between neighbouring electrodes are listed in Table 3.
  • Pretreatment with an aqueous solution of sodium tartrate provided limited restraint as shown by the reduced growth of the silver dendrite front.
  • Pretreatment with high concentrations of sodium sulphide appeared to detach the silver dendrite front from the electrode.
  • Low concentrations of 5- methyl-s-triazolo[l,5-a]pyrimidin-7-ol also restrained silver dendrite growth as evidenced by the break up of the silver dendrite front into clusters of silver dendrites although this was limited to particular zones .
  • 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.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)
  • Thin Film Transistor (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une couche conductrice sensiblement transparente appliquée sur un support, ladite couche comprenant par exemple un polymère intrinsèquement conducteur contenant éventuellement des motifs structuraux représentés par la formule(I) dans laquelle n est supérieur à 1 et chaque radical R1 et R2 représente indépendamment l'un de l'autre hydrogène ou un groupe alkyle C1-4 éventuellement substitué ou bien R1 et R2 représentent conjointement un groupe alkylène C1-4 éventuellement substitué ou un groupe cycloalkylène éventuellement substitué, de préférence un groupe éthylène, un groupe méthylène éventuellement substitué par alkyle, un groupe éthylène éventuellement substitué par phényle ou alkyle C1-12, un groupe 1,3-propylène ou un groupe 1,2-cyclohexylène ; et un métal conducteur réparti de manière non uniforme à l'intérieur de ladite couche et formant une entité conductrice. L'invention concerne également un procédé pour préparer ladite couche conductrice transparente, ainsi que des diodes électroluminescentes, des dispositifs photovoltaïques, des transistors et des dispositifs électroluminescents comprenant ladite couche conductrice.
EP02807724A 2002-08-22 2002-08-22 Procede pour preparer une couche conductrice sensiblement transparente Ceased EP1532640A1 (fr)

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US7138170B2 (en) * 2003-04-28 2006-11-21 Eastman Kodak Company Terminated conductive patterned sheet utilizing conductive conduits
US7351358B2 (en) 2004-03-17 2008-04-01 E.I. Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
US7354532B2 (en) 2004-04-13 2008-04-08 E.I. Du Pont De Nemours And Company Compositions of electrically conductive polymers and non-polymeric fluorinated organic acids
JP2006116806A (ja) * 2004-10-21 2006-05-11 Jsr Corp 複合フィルム、その製造方法および電極
WO2007002737A2 (fr) 2005-06-28 2007-01-04 E. I. Du Pont De Nemours And Company Conducteurs transparents a travail d'extraction eleve
GB0518611D0 (en) * 2005-09-13 2005-10-19 Eastman Kodak Co Transparent conductive system
KR101039543B1 (ko) 2006-09-28 2011-06-09 후지필름 가부시키가이샤 자발광 표시 장치, 자발광 표시 장치의 제조 방법, 투명 도전성 필름, 전계 발광 소자, 태양 전지용 투명 전극 및 전자 페이퍼용 투명 전극
US20080191172A1 (en) 2006-12-29 2008-08-14 Che-Hsiung Hsu High work-function and high conductivity compositions of electrically conducting polymers
SG175925A1 (en) 2009-05-15 2011-12-29 Novartis Ag Aryl pyridine as aldosterone synthase inhibitors

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JP2006501604A (ja) 2006-01-12

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