EP2311047A1 - Dispersions aqueuses de polymères électriquement conducteurs contenant des nanoparticules inorganiques - Google Patents

Dispersions aqueuses de polymères électriquement conducteurs contenant des nanoparticules inorganiques

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Publication number
EP2311047A1
EP2311047A1 EP09800711A EP09800711A EP2311047A1 EP 2311047 A1 EP2311047 A1 EP 2311047A1 EP 09800711 A EP09800711 A EP 09800711A EP 09800711 A EP09800711 A EP 09800711A EP 2311047 A1 EP2311047 A1 EP 2311047A1
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EP
European Patent Office
Prior art keywords
composition
oxide
group
layer
fluorinated
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.)
Withdrawn
Application number
EP09800711A
Other languages
German (de)
English (en)
Other versions
EP2311047A4 (fr
Inventor
Che-Hsiung Hsu
Hong Meng
Hjalti Skulason
Jonathan M. Ziebarth
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority claimed from PCT/US2008/070718 external-priority patent/WO2009018009A1/fr
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2311047A1 publication Critical patent/EP2311047A1/fr
Publication of EP2311047A4 publication Critical patent/EP2311047A4/fr
Withdrawn legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
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    • 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
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/512—Hole transport
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer

Definitions

  • This disclosure relates in general to electrically conductive polymer compositions containing inorganic nanoparticles, and their use in electronic devices. Description of the Related Art
  • Organic electronic devices define a category of products that include an active layer.
  • Organic electronic devices have at least one organic active layer. Such devices convert electrical energy into radiation such as light emitting diodes, detect signals through electronic processes, convert radiation into electrical energy, such as photovoltaic cells, or include one or more organic semiconductor layers.
  • OLEDs are an organic electronic device comprising an organic layer capable of electroluminescence.
  • OLEDs containing conducting polymers can have the following configuration:
  • the anode is typically any material that has the ability to inject holes into the EL material, such as, for example, indium/tin oxide (ITO).
  • ITO indium/tin oxide
  • the anode is optionally supported on a glass or plastic substrate.
  • EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof.
  • the cathode is typically any material (such as, e.g., Ca or Ba) that has the ability to inject electrons into the EL material.
  • Electrically conducting polymers having low conductivity in the range of 10 -3 to 10 '7 S/cm are commonly used as the buffer layer in direct contact with an electrically conductive, inorganic oxide anode such as ITO.
  • composition comprising an aqueous dispersion of at least one electrically conductive polymer doped with at least one highly-fluorinated acid polymer, and having inorganic nanoparticles dispersed therein.
  • electronic devices comprising at least one layer comprising the above film are provided.
  • Figure 1 is a schematic diagram of an organic electronic device.
  • conductor and its variants are intended to refer to a layer material, member, or structure having an electrical property such that current flows through such layer material, member, or structure without a substantial drop in potential.
  • the term is intended to include semiconductors.
  • a conductor will form a layer having a conductivity of at least 10 -7 S/cm.
  • electrically conductive as it refers to a material, is intended to mean a material which is inherently or intrinsically capable of electrical conductivity without the addition of carbon black or conductive metal particles.
  • polymer is intended to mean a material having at least one repeating monomeric unit.
  • the term includes homopolymers having only one kind, or species, of monomeric unit, and copolymers having two or more different monomeric units, including copolymers formed from monomeric units of different species.
  • acid polymer refers to a polymer having acidic groups.
  • acidic group refers to a group capable of ionizing to donate a hydrogen ion to a Br ⁇ nsted base.
  • highly-fluorinated refers to a compound in which at least 90% of the available hydrogens bonded to carbon have been replaced by fluorine.
  • the composition may comprise one or more different electrically conductive polymers and one or more different highly-fluorinated acid polymers.
  • doped as it refers to an electrically conductive polymer, is intended to mean that the electrically conductive polymer has a polymeric counterion to balance the charge on the conductive polymer.
  • doped conductive polymer is intended to mean the conductive polymer and the polymeric counterion that is associated with it.
  • layer is used interchangeably with the term “film” and refers to a coating covering a desired area.
  • the term is not limited by size.
  • the area can be as large as an entire device or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel.
  • Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.
  • nanoparticle refers to a material having a particle size less than 100 nm. In some embodiments, the particle size is less than 10 nm. In some embodiments, the particle size is less than 5 nm.
  • aqueous refers to a liquid that has a significant portion of water, and in one embodiment it is at least about 40% by weight water; in some embodiments, at least about 60% by weight water.
  • hole transport when referring to a layer, material, member, or structure, is intended to mean such layer, material, member, or structure facilitates migration of positive charges through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge.
  • electron transport means when referring to a layer, material, member or structure, such a layer, material, member or structure that promotes or facilitates migration of negative charges through such a layer, material, member or structure into another layer, material, member or structure.
  • Organic electronic device is intended to mean a device including one or more semiconductor layers or materials.
  • Organic electronic devices include, but are not limited to: (1 ) devices that convert electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, diode laser, or lighting panel), (2) devices that detect signals through electronic processes (e.g., photodetectors photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, infrared (“IR”) detectors, or biosensors), (3) devices that convert radiation into electrical energy (e.g., a photovoltaic device or solar cell), and (4) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., a transistor or diode).
  • IR infrared
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • any electrically conductive polymer can be used in the new composition.
  • the electrically conductive polymer will form a film which has a conductivity greater than 10 ⁇ 7 S/cm.
  • the conductive polymers suitable for the new composition are made from at least one monomer which, when polymerized alone, forms an electrically conductive homopolymer. Such monomers are referred to herein as "conductive precursor monomers.” Monomers which, when polymerized alone form homopolymers which are not electrically conductive, are referred to as "non-conductive precursor monomers.”
  • the conductive polymer can be a homopolymer or a copolymer.
  • Conductive copolymers suitable for the new composition can be made from two or more conductive precursor monomers or from a combination of one or more conductive precursor monomers and one or more non-conductive precursor monomers.
  • the conductive polymer is made from at least one conductive precursor monomer selected from thiophenes, pyrroles, anilines, and polycyclic aromatics.
  • polycyclic aromatic refers to compounds having more than one aromatic ring. The rings may be joined by one or more bonds, or they may be fused together.
  • aromatic ring is intended to include heteroaromatic rings.
  • a "polycyclic heteroaromatic” compound has at least one heteroaromatic ring.
  • the conductive polymer is made from at least one precursor monomer selected from thiophenes, selenophenes, tellurophenes, pyrroles, anilines, and polycyclic aromatics.
  • the polymers made from these monomers are referred to herein as polythiophenes, poly(selenoph ⁇ nes), poly(tellurophenes), polypyrroles, polyanilines, and polycyclic aromatic polymers, respectively.
  • polycyclic aromatic refers to compounds having more than one aromatic ring. The rings may be joined by one or more bonds, or they may be fused together.
  • aromatic ring is intended to include heteroaromatic rings.
  • a "polycyclic heteroaromatic” compound has at least one heteroaromatic ring.
  • the polycyclic aromatic polymers are poly(thienothiophenes).
  • monomers contemplated for use to form the electrically conductive polymer in the new composition comprise Formula I below:
  • Q is selected from the group consisting of S, Se, and Te;
  • R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or al
  • alkyl refers to a group derived from an aliphatic hydrocarbon and includes linear, branched and cyclic groups which may be unsubstituted or substituted.
  • heteroalkyl is intended to mean an alkyl group, wherein one or more of the carbon atoms within the alkyl group has been replaced by another atom, such as nitrogen, oxygen, sulfur, and the like.
  • alkylene refers to an alkyl group having two points of attachment.
  • alkenyl refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, and includes linear, branched and cyclic groups which may be unsubstituted or substituted.
  • heteroalkenyl is intended to mean an alkenyl group, wherein one or more of the carbon atoms within the alkenyl group has been replaced by another atom, such as nitrogen, oxygen, sulfur, and the like.
  • alkenylene refers to an alkenyl group having two points of attachment.
  • R 3 is a single bond or an alkylene group
  • R 4 is an alkylene group
  • R 5 is an alkyl group
  • R 6 is hydrogen or an alkyl group p is O or an integer from 1 to 20 Z is H, alkali metal, alkaline earth metal, N(R 5 J 4 or R 5 Any of the above groups may further be unsubstituted or substituted, and any group may have F substituted for one or more hydrogens, including perfluorinated groups.
  • the alkyl and alkylene groups have from 1-20 carbon atoms.
  • both R 1 together form — W- (CY 1 YVw- , where m is 2 or 3, W is O, S, Se, PO 1 NR 6 , Y 1 is the same or different at each occurrence and is hydrogen or fluorine, and Y 2 is the same or different at each occurrence and is selected from hydrogen, halogen, alkyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, where the Y groups may be partially or fully fluorinated. In some embodiments, all Y are hydrogen.
  • the polymer is poly(3,4- ethylenedioxythiophene).
  • at least one Y group is not hydrogen.
  • at least one Y group is a substituent having F substituted for at least one hydrogen.
  • at least one Y group is perfluorinated.
  • the monomer has Formula l(a):
  • Q is selected from the group consisting of S, Se, and Te;
  • R 7 is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, with the proviso that at least one R 7 is not hydrogen, and m is 2 or 3.
  • m is two, one R 7 is an alkyl group of more than 5 carbon atoms, and all other R 7 are hydrogen. In some embodiments of Formula l(a), at least one R 7 group is fluorinated. In some embodiments, at least one R 7 group has at least one fluorine substituent. In some embodiments, the R 7 group is fully fluorinated.
  • the R 7 substituents on the fused alicyclic ring on the monomer offer improved solubility of the monomers in water and facilitate polymerization in the presence of the fluorinated acid polymer.
  • m is 2, one R 7 is sulfonic acid-propylene-ether-methylene and all other R 7 are hydrogen. In some embodiments, m is 2, one R 7 is propyl-ether-ethylene and all other R 7 are hydrogen. In some embodiments, m is 2, one R 7 is methoxy and all other R 7 are hydrogen. In some embodiments, one R 7 is sulfonic acid difluoromethylene ester methylene (-CH2-O-C(O)-CF2-SO3H), and all other R 7 are hydrogen.
  • pyrrole monomers contemplated for use to form the electrically conductive polymer in the new composition comprise Formula Il below.
  • R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxy!, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or al
  • R 1 is the same or different at each occurrence and is independently selected from hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, urethane, epoxy, silane, siloxane, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxy I, epoxy, silane, or siloxane moieties.
  • R 2 is selected from hydrogen, alkyl, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moieties.
  • the pyrrole monomer is unsubstituted and both R 1 and R 2 are hydrogen.
  • both R 1 together form a 6- or 7-membered alicyclic ring, which is further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. These groups can improve the solubility of the monomer and the resulting polymer.
  • both R 1 together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group.
  • both R 1 together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group having at least 1 carbon atom.
  • both R 1 together form -O-(CHY) m "O- , where m is 2 or 3, and Y is the same or different at each occurrence and is selected from hydrogen, alkyl, alcohol, benzyl, carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.
  • at least one Y group is not hydrogen.
  • at least one Y group is a substituent having F substituted for at least one hydrogen.
  • at least one Y group is perfluorinated.
  • aniline monomers contemplated for use to form the electrically conductive polymer in the new composition comprise Formula III below.
  • R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxy I, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate
  • the aniline monomelic unit can have Formula IV(a) or Formula I V(b) shown below, or a combination of both formulae.
  • a is not 0 and at least one R 1 is fluorinated. In some embodiments, at least one R 1 is perfluorinated.
  • fused polycylic heteroaromatic monomers contemplated for use to form the electrically conductive polymer in the new composition have two or more fused aromatic rings, at least one of which is heteroaromatic.
  • the fused polycyclic heteroaromatic monomer has Formula V:
  • Q is S, Se 1 Te, or NR 6 ;
  • R 6 is hydrogen or alkyl
  • R 8 , R 9 , R 10 , and R 11 are independently selected so as to be the same or different at each occurrence and are selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioaikyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, aryls ⁇ lfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate,
  • the fused polycyclic heteroaromatic monomer has a formula selected from the group consisting of Formula V(a), V(b), V(C), V(d), V(e), V(f), V(g), V(h), V(i), V(J), and V(k):
  • Q is S, Se, Te, or NH
  • T is the same or different at each occurrence and is selected from S, NR 6 , O, SiR 6 2, Se, Te, and PR 6 ;
  • Y is N
  • R 6 is hydrogen or alkyl.
  • the fused polycyclic heteroaromatic monomers may be further substituted with groups selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.
  • the substituent groups are fluorinated. In some embodiments, the substituent groups are fully fluorinated.
  • the fused polycyclic heteroaromatic monomer is a thieno(thiophene).
  • thieno(thiophene) is selected from thieno(2,3-b)thiophene, thieno(3,2- b)thiophene, and thieno(3,4-b)thiophene.
  • the thieno(thiophene) monomer is further substituted with at least one group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.
  • the substituent groups are fluorinated. In some embodiments, the substituent groups are fully fluorinated.
  • polycyclic heteroaromatic monomers contemplated for use to form the polymer in the new composition comprise Formula Vl: wherein:
  • Q is S, Se, Te 1 or NR 6 ;
  • T is selected from S, NR 6 , O, SiR 6 2 , Se, Te, and PR 6 ;
  • E is selected from alkenylene, arylene, and heteroarylene
  • R 6 is hydrogen or alkyl
  • R 12 is the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 12 groups together may form an alkylene or alken
  • the electrically conductive polymer is a copolymer of a precursor monomer and at least one second monomer. Any type of second monomer can be used, so long as it does not detrimentally affect the desired properties of the copolymer.
  • the second monomer comprises no more than 50% of the polymer, based on the total number of monomer units. In some embodiments, the second monomer comprises no more than 30%, based on the total number of monomer units. In some embodiments, the second monomer comprises no more than 10%, based on the total number of monomer units.
  • Exemplary types of second monomers include, but are not limited to, alkenyl, alkynyl, arylene, and heteroarylene.
  • Examples of second monomers include, but are not limited to, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylenevinylene, phenyleneethynylene, pyridine, diazines, and triazines, all of which may be further substituted.
  • the copolymers are made by first forming an intermediate precursor monomer having the structure A-B-C 1 where A and C represent precursor monomers, which can be the same or different, and B represents a second monomer.
  • the A-B-C intermediate precursor monomer can be prepared using standard synthetic organic techniques, such as Yamamoto, StHIe. Grignard metathesis, Suzuki, and Negishi couplings.
  • the copolymer is then formed by oxidative polymerization of the intermediate precursor monomer alone, or with one or more additional precursor monomers.
  • the electrically conductive polymer is selected from the group consisting of a polythiophene, a polypyrrole, a polymeric fused polycyclic heteroaromatic, a copolymer thereof, and combinations thereof.
  • the electrically conductive polymer is selected from the group consisting of poly(3,4-ethylenedioxythiophene) l unsubstituted polypyrrole, poly(thieno(2,3-b)thiophene), poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene).
  • the highly-fluorinated acid polymer can be any polymer which is highly-fluorinated and has acidic groups with acidic protons.
  • the acidic groups supply an ionizable proton.
  • the acidic proton has a pKa of less than 3.
  • the acidic proton has a pKa of less than 0.
  • the acidic proton has a pKa of less than -5.
  • the acidic group can be attached directly to the polymer backbone, or it can be attached to side chains on the polymer backbone.
  • acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof.
  • the acidic groups can all be the same, or the polymer may have more than one type of acidic group.
  • the acidic groups are selected from the group consisting of sulfonic acid groups, sulfonamide groups, and combinations thereof.
  • the HFAP is at least 95% fluorinated; in some embodiments, fully-fluorinated.
  • the HFAP is water-soluble. In some embodiments, the HFAP is dispersible in water. In some embodiments, the HFAP is organic solvent wettable.
  • organic solvent wettable refers to a material which, when formed into a film, possesses a contact angle no greater than 60°C with organic solvents. . In some embodiments, wettable materials form films which are wettable by phenylhexane with a contact angle no greater than 55°. The methods for measuring contact angles are well known. In some embodiments, the wettable material can be made from a polymeric acid that, by itself is non- wettable, but with selective additives it can be made wettable.
  • suitable polymeric backbones include, but are not limited to, polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, and copolymers thereof, all of which are highly-fluorinated; in some embodiments, fully- fluorinated.
  • the acidic groups are sulfonic acid groups or sulfonimide groups.
  • a sulfonimide group has the formula:
  • the acidic groups are on a fluorinated side chain.
  • the fluorinated side chains are selected from alkyl groups, alkoxy groups, amido groups, ether groups, and combinations thereof, all of which are fully fluorinated.
  • the HFAP has a highly-fluorinated olefin backbone, with pendant highly-fluorinated alkyl sulfonate, highly- fluorinated ether sulfonate, highly-fluorinated ester sulfonate, or highly- fluorinated ether sulfonimide groups.
  • the HFAP is a perfluoroolefin having perfluoro-ether-sulfonic acid side chains.
  • the polymer is a copolymer of 1 ,1-difluoroethylene and 2- (1 ,1-difluoro2-(trifluoromethyl)allyloxy)-1 ,1 ,2,2-tetrafluoroethanesulfonic acid.
  • the polymer is a copolymer of ethylene and 2- (2-(1,2,2-trifluorovinyloxy)-1 l 1 ,2,3,3,3-hexafluoropropoxy)-1, 1,2,2- tetrafluoroethanesulfonic acid. These copolymers can be made as the corresponding sulfonyl fluoride polymer and then can be converted to the sulfonic acid form.
  • the HFAP is homopolymer or copolymer of a fluorinated and partially sulfonated poly(arylene ether sulfone).
  • the copolymer can be a block copolymer.
  • the HFAP is a sulfonimide polymer having Formula IX:
  • R f is selected from highly-fluorinated alkylene, highly-fluorinated heteroalkyl ⁇ ne, highly-fluorinated arylene, and highly-fluorinated heteroarylene, which may be substituted with one or more ether oxygens; and n is at least 4.
  • Rf is a perfluoroalkyl group. In one embodiment, R f is a perfluorobutyl group. In one embodiment, R f contains ether oxygens. In one embodiment n is greater than 10.
  • the HFAP comprises a highly-fluorinated polymer backbone and a side chain having Formula X: where: R 15 is a highly-fluorinated alkylene group or a highly-fluorinated heteroalkylene group;
  • R 16 is a highly-fluorinated alkyl or a highly-fluorinated aryl group; and a is 0 or an integer from 1 to 4.
  • the HFAP has Formula Xl:
  • R 16 is a highly-fluorinated alkyl or a highly-fluorinated aryl group; c is independently O or an integer from 1 to 3; and n is at least 4.
  • the HFAP also comprises a repeat unit derived from at least one highly-fluorinated ethylenically unsaturated compound.
  • the perfluoroolefin comprises 2 to 20 carbon atoms.
  • the comonomer is tetrafluoroethylene.
  • the HFAP is a colloid-forming polymeric acid.
  • colloid-forming refers to materials which are insoluble in water, and form colloids when dispersed into an aqueous medium.
  • the colloid-forming polymeric acids typically have a molecular weight in the range of about 10,000 to about 4,000,000. In one embodiment, the polymeric acids have a molecular weight of about 100,000 to about 2,000,000.
  • Colloid particle size typically ranges from 2 nanometers (nm) to about 140 nm. In one embodiment, the colloids have a particle size of 2 nm to about 30 nm.
  • any highly-fluorinated colloid- forming polymeric material having acidic protons can be used.
  • Some of the polymers described hereinabove may be formed in non-acid form, e.g., as salts, esters, or sulfonyl fluorides. They will be converted to the acid form for the preparation of conductive compositions, described below.
  • E 5 can be a cation such as Li, Na, or K, and be converted to the acid form.
  • the HFAP can be the polymers disclosed in U.S. Patent No. 3,282,875 and in U.S. Patent Nos. 4,358,545 and 4,940,525.
  • the HFAP comprises a perfluorocarbon backbone and the side chain represented by the formula -O-CF 2 CF(CF 3 )-O-CF 2 CF 2 SO 3 E 5 where E 5 is as defined above.
  • CF 2 CF(CF 3 )-O-CF 2 CF 2 SO 2 F perfluoro(3,6-dioxa-4-methyl-7- octenesulfonyl fluoride) (PDMOF), followed by conversion to sulfonate groups by hydrolysis of the sulfonyl fluoride groups and ion exchanged as necessary to convert them to the desired ionic form.
  • PMOF perfluoro(3,6-dioxa-4-methyl-7- octenesulfonyl fluoride)
  • PMOF perfluoro(3,6-dioxa-4-methyl-7- octenesulfonyl fluoride)
  • PMOF perfluoro(3,6-dioxa-4-methyl-7- octenesulfonyl fluoride)
  • sulfonate groups by hydrolysis of the sulfonyl fluoride groups and ion exchanged as necessary to convert
  • HFAP is available commericially as aqueous Nafion® dispersions, from E. I. du Pont de Nemours and Company (Wilmington, DE). 4. Inorganic Nanoparticles
  • the inorganic nanoparticles can be insulative or semiconductive.
  • the inorganic nanoparticles are metal sulfides or metal oxides.
  • semiconductive metal oxides include, but are not limited to mixed valence metal oxides, such as zinc antimonates, and non-stoichiometric metal oxides, such as oxygen deficient molybdenum trioxide, vanadium pentoxide, and the like.
  • Zinc antimonates, ZnO/Sb 2 O 5 are commercially available from Nissan Chemical Company under the trade name "Celnax" in a variety of ratios (see, for example, US Patent 5,707,552).
  • insulative metal oxides include, but are not limited to, silicon oxide, titanium oxides, zirconium oxide, molybdenum trioxide, vanadium oxide, aluminum oxide, zinc oxide, samarium oxide, yttrium oxide, cesium oxide, cupric oxide, stannic oxide, antimony oxide, and the like.
  • metal sulfides examples include cadmium sulfide, copper sulfide, lead sulfide, mercury sulfide, indium sulfide, silver sulfide, cobalt sulfide, nickel sulfide, and molybdenum sulfide.
  • Mixed metal sulfides such as Ni/Cd sulfides, Co/Cd sulfides, Cd/ln sulfides, and Pd-Co-Pd sulfides may be used.
  • the metal nanoparticles may contain both sulfur and oxygen. In some embodiments, combinations of metal nanoparticles are used.
  • Metal oxide nanoparticles can be made by reactive sputtering of metal in the presence of oxygen, evaporation of selected oxide, and multi-component oxides, or by vapor-phase hydrolysis of inorganic compounds, for example silicon tetrachloride. It can also be produced by sol-gel chemistry using hydrolyzable metal compounds, particularly alkoxides of various elements, to react with either by hydrolysis and polycondensation to form multi-component and multidimensional network oxides.
  • Metal sulfide nanoparticles can be obtained by various chemical and physical methods. Some examples of physical methods are vapor deposition, lithographic processes and molecular beam epitaxy (MBE) of metal sulfides such as cadmium sulfide, (CdS), lead sulfide (PbS), zinc sulfide (ZnS), silver sulfide (Ag 2S), molybdenum sulfide (MoS 2) etc.
  • Chemical methods for the preparation of metal sulfide nanoparticles are based on the reaction of metal ions in solution either with H 2 S gas or Na 2 S in aqueous medium.
  • the nano-particles are surface-treated with a coupling agent to be compatible with the aqueous electrically conducting polymers.
  • the class of surface modifiers includes, but not limited to silanes, titanates, zirconates, aluminate and polymeric dispersant.
  • the surface modifiers contain chemical functionality, examples of which include, but are not limited, to nitrile, amino, cyano, alkyl amino, alkyl, aryl, alkenyl, alkoxy, aryloxy, sulfonic acid, acrylic acid, phosphoric acid, and alkali salts of the above acids, acrylate, sulfonates, amidosulfonate, ether, ether sulfonate, estersulfonate, alkylthio, and arylthio.
  • the chemical functionality may include a crosslinker such as epoxy, alkylvinyl and arylvinyl group to react with the the conducting polymer in the nanc-composite or hole-transporting material on the next upper layer.
  • the surface modifiers are fluorinated, or pefluorinated, such as tetrafiuoro-ethyltrifluoro-vinyl-ether triethoxysilane, perfluorobutane-triethoxysilane, perfluorooctyltriethoxysilane, bis(trifluoropropyl)-tetramethyldisilazane, and bis (3-triethoxysilyl)propyl tetrasulfide.
  • the new electrically conductive polymer composition is prepared by first forming the doped conductive polymer and then adding the inorganic nanoparticles.
  • the doped electrically conductive polymer is formed by oxidative polymerization of the precursor monomer in the presence of the HFAP in an aqueous medium.
  • the polymerization has been described in published U.S. patent applications 2004/0102577, 2004/0127637, and 2005/205860.
  • the inorganic nanoparticles can be added to the doped conductive polymer dispersion directly as a solid.
  • the inorganic nanoparticles are dispersed in an aqueous solution, and this dispersion is mixed with the doped conductive polymer dispersion.
  • the weight ratio of nanoparticles to electrically conductive polymer is in the range of 0.1 to 10.0.
  • the pH is increased either prior to the addition of the inorganic particles or after.
  • the dispersions of doped conductive polymer and inorganic nanoparticles remain stable from the as- formed phi of about 2, to neutral pH.
  • the pH can be adjusted by treatment with cation exchange resins prior to nanoparticle addition.
  • the pH is adjusted by the addition of aqueous base solution.
  • Cations for the base can be, but are not limited to, alkali metal, alkaline earth metal, ammonium, and alkylammonium. In some embodiments, alkali metal is preferred over alkaline earth metal cations.
  • Films made from the new conductive composition described herein are hereinafter referred to as "the new films described herein".
  • the films can be made using any liquid deposition technique, including continuous and discontinuous techniques.
  • Continuous deposition techniques include but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating.
  • Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
  • buffer layers deposited from aqueous dispersions comprising the new conductive polymer composition.
  • the term "buffer layer” or “buffer material” is intended to mean electrically conductive or semiconductive materials and may have one or more functions in an organic electronic device, including but not limited to, planarization of the underlying layer, charge transport and/or charge injection properties, scavenging of impurities such as oxygen or metal ions, and other aspects to facilitate or to improve the performance of the organic electronic device.
  • layer is used interchangeably with the term “film” and refers to a coating covering a desired area.
  • the term is not limited by size.
  • the area can be as large as an entire device or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel.
  • Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.
  • Continuous deposition techniques inlcude but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating.
  • Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
  • the dried films of the new conductive polymer composition are generally not redispersible in water.
  • the buffer layer can be applied as multiple thin layers.
  • the buffer layer can be overcoated with a layer of different water-soluble or water-dispersible material without being damaged.
  • Buffer layers comprising the new conductive polymer composition have been surprisingly found to have improved wettability.
  • films made from the new conductive polymer composition exhibit a contact angle with organic solvents of less than 50°.
  • the films are wettable with p-xylene with a contact angle less than 50°; in some embodiments, less than 40°; in some embodiments, less than 30°.
  • buffer layers deposited from aqueous dispersions comprising the new conductive polymer composition blended with other water soluble or dispersible materials.
  • materials which can be added include, but are not limited to polymers, dyes, coating aids, organic and inorganic conductive inks and pastes, charge transport materials, crosslinking agents, and combinations thereof.
  • the other water soluble or dispersible materials can be simple molecules or polymers.
  • suitable polymers include, but are not limited to, conductive polymers such as polythiophenes, polyanilines, polypyrroles, polyacetylenes, poly(thienothiophenes), and combinations thereof. 7. Electronic Devices
  • electroactive layer when referring to a layer or material is intended to mean a layer or material that exhibits electronic or electro-radiative properties.
  • An electroactive layer material may emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation.
  • a typical device, 100 has an anode layer 110, a buffer layer 120, an electroactive layer 130, and a cathode layer 150. Adjacent to the cathode layer 150 is an optional electron- injection/transport layer 140.
  • the device may include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 150. Most frequently, the support is adjacent to the anode layer 110.
  • the support can be flexible or rigid, organic or inorganic. Examples of support materials include, but are not limited to, glass, ceramic, metal, and plastic films.
  • the anode layer 110 is an electrode that is more efficient for injecting holes compared to the cathode layer 150.
  • the anode can include materials containing a metal, mixed metal, alloy, metal oxide or mixed oxide. Suitable materials include the mixed oxides of the Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11 elements, the elements in Groups 4, 5, and 6, and the Group 8-10 transition elements. If the anode layer 110 is to be light transmitting, mixed oxides of Groups 12, 13 and 14 elements, such as indium-tin-oxide, may be used. As used herein, the phrase "mixed oxide” refers to oxides having two or more different cations selected from the Group 2 elements or the Groups 12, 13, or 14 elements.
  • anode layer 110 examples include, but are not limited to, indium-tin-oxide ("ITO"), indium-zinc-oxide, aluminum-tin-oxide, gold, silver, copper, and nickel.
  • the anode may also comprise an organic material, especially a conducting polymer such as polyaniline, including exemplary materials as described in "Flexible light-emitting diodes made from soluble conducting polymer," Nature vol. 357, pp 477479 (11 June 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.
  • the anode layer 110 may be formed by a chemical or physical vapor deposition process or spin-cast process.
  • Chemical vapor deposition may be performed as a plasma-enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("MOCVD”).
  • Physical vapor deposition can include all forms of sputtering, including ion beam sputtering, as well as e-beam evaporation and resistance evaporation.
  • Specific forms of physical vapor deposition include rf magnetron sputtering and inductively-coupled plasma physical vapor deposition ("IMP-PVD"). These deposition techniques are well known within the semiconductor fabrication arts.
  • the anode layer 110 is patterned during a lithographic operation.
  • the pattern may vary as desired.
  • the layers can be formed in a pattern by, for example, positioning a patterned mask or resist on the first flexible composite barrier structure prior to applying the first electrical contact layer material.
  • the layers can be applied as an overall layer (also called blanket deposit) and subsequently patterned using, for example, a patterned resist layer and wet chemical or dry etching techniques. Other processes for patterning that are well known in the art can also be used.
  • the buffer layer 120 comprises the new conductive composition described herein.
  • Buffer layers made from conductive polymers doped with HFAPs generally are not wettable by organic solvents and have a refractive index below 1.4 (@460nm wavelength).
  • the buffer layers described herein can be more wettable and thus are more easily coated with the next layer from a non-polar organic solvent.
  • the buffer layers described herein also can have a refractive index greater than 1.4 (@460nm).
  • the buffer layer is usually deposited onto substrates using a variety of techniques well-known to those skilled in the art. Typical deposition techniques, as discussed above, include vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.
  • An optional layer, not shown, may be present between the buffer layer 120 and the electroactive layer 130.
  • This layer may comprise hole transport materials. Examples of hole transport materials have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting molecules and polymers can be used.
  • hole transporting molecules include, but are not limited to: 4,4 ⁇ 4"-tris(N, N- diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tris(N-3-methylphenyl-N- phenyl-amino)-triphenylamine (MTDATA); N.N'-diphenyl-N.N'-bis(3- methylphenylHI.I'-biphenyl]-4,4'-diamine (TPD); 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)-N,N'-bis(4- ethylphenyl)-[1 ,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); tetrakis-(3- methylphenyl)-N,N,N',N
  • hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes), polyanilines, and polypyrroles. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
  • the electroactive layer 130 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
  • the electroactive material is an organic electroluminescent ("EL") material. Any EL material can be used in the devices, including, but not limited to, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof.
  • fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof.
  • metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated indium and platinum electroluminescent compounds, such as complexes of indium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., U.S.
  • Electroluminescent emissive layers comprising a charge carrying host material and a metal complex have been described by Thompson et al., in U.S. Patent 6,303,238, and by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512.
  • conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymers thereof, and mixtures thereof.
  • Optional layer 140 can function both to facilitate electron injection/transport, and can also serve as a confinement layer to prevent quenching reactions at layer interfaces. More specifically, layer 140 may promote electron mobility and reduce the likelihood of a quenching reaction if layers 130 and 150 would otherwise be in direct contact.
  • Examples of materials for optional layer 140 include, but are not limited to, metal chelated oxinoid compounds, such as bis(2-methyl-8- quinolinolato)(para-phenyl-phenolato)aluminurn(lll) (BAIQ) and tris(8-hydroxyquinolato)aluminum (Alq3); tetrakis(8- hydroxyquinolinato)zirconium; azole compounds such as 2-(4-biphenylyl)- 5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4- t-butylphenyl)-1,2,4-triazole (TAZ), and 1 ,3,5-tri(phenyl-2- benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4- fluoroph ⁇ nyl)quinoxaline; phenanthro
  • the cathode layer 150 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
  • the cathode layer 150 can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, the anode layer 110).
  • the term "lower work function” is intended to mean a material having a work function no greater than about 4.4 eV.
  • “higher work function” is intended to mean a material having a work function of at least approximately 4.4 eV.
  • Materials for the cathode layer can be selected from alkali metals of Group 1 (e.g., Li, Na, K, Rb, Cs 1 ), the Group 2 metals (e.g., Mg, Ca, Ba, or the like), the Group 12 metals, the lanthanides (e.g., Ce, Sm, Eu, or the like), and the actinides (e.g., Th, U, or the like). Materials such as aluminum, indium, yttrium, and combinations thereof, may also be used.
  • Group 1 e.g., Li, Na, K, Rb, Cs 1
  • the Group 2 metals e.g., Mg, Ca, Ba, or the like
  • the lanthanides e.g., Ce, Sm, Eu, or the like
  • actinides e.g., Th, U, or the like.
  • Materials such as aluminum, indium, yttrium, and combinations thereof, may also be used.
  • cathode layer 150 examples include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof.
  • the cathode layer 150 is usually formed by a chemical or physical vapor deposition process. In some embodiments, the cathode layer will be patterned, as discussed above in reference to the anode layer 110.
  • Other layers in the device can be made of any materials which are known to be useful in such layers upon consideration of the function to be served by such layers.
  • an encapsulation layer (not shown) is deposited over the contact layer 150 to prevent entry of undesirable components, such as water and oxygen, into the device 100. Such components can have a deleterious effect on the organic layer 130.
  • the encapsulation layer is a barrier layer or film.
  • the encapsulation layer is a glass lid.
  • the device 100 may comprise additional layers. Other layers that are known in the art or otherwise may be used. In addition, any of the above-described layers may comprise two or more sub-layers or may form a laminar structure. Alternatively, some or all of anode layer 110 the hole transport layer 120, the electron transport layer 140, cathode layer 150, and other layers may be treated, especially surface treated, to increase charge carrier transport efficiency or other physical properties of the devices.
  • the choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency with device operational lifetime considerations, fabrication time and complexity factors and other considerations appreciated by persons skilled in the art. It will be appreciated that determining optimal components, component configurations, and compositional identities would be routine to those of ordinary skill of in the art.
  • the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000A; buffer layer 120, 50-2000 A, in one embodiment 200-1000 A; photoactive layer 130, 10-2000 A, in one embodiment 100-1000 A; optional electron transport layer 140, 50-2000 A, in one embodiment 100-1000 A; cathode 150, 200-10000 A, in one embodiment 300-5000 A.
  • the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device can be affected by the relative thickness of each layer.
  • the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone is in the light-emitting layer.
  • the desired ratio of layer thicknesses will depend on the exact nature of the materials used.
  • a voltage from an appropriate power supply (not depicted) is applied to the device 100.
  • Current therefore passes across the layers of the device 100. Electrons enter the organic polymer layer, releasing photons.
  • OLEDs 1 called active matrix OLED displays individual deposits of photoactive organic films may be independently excited by the passage of current, leading to individual pixels of light emission.
  • OLEDs 1 called passive matrix OLED displays deposits of photoactive organic films may be excited by rows and columns of electrical contact layers.
  • Comparative Example A This comparative example illustrates low electrical conductivity and non-wettability of PAni/Nafion®, poly(tetrafluoroethylene)/ perfluoroethersulfonic acid, films, without added inorganic nanoparticles.
  • a PAni/Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion having an EW (acid equivalent weight) of 1000.
  • the Nafion® dispersion at 25% (w/w) was made using a procedure similar to the procedure in U.S. Patent No. 6,150,426, Example 1, Part 2, except that the temperature was approximately 270°C and was then diluted with water to form a 12.0% (w/w) dispersion for the polymerization.
  • One portion was kept as-is without addition of a base. This portion was determined to have pH of 2, and contain 2.88% (w/w) PAni/Nafion®.
  • Thin films were prepared from the PAni/Nafion® and subsequently baked at 130°C in air. Room temperature electrical conductivity of the thin films was determined to be 1,2x10 -8 S/cm, which is also shown in Table 1.
  • One small drop of toluene was placed on one piece of thin film, but the toluene quickly rolled off the film, which indicates that the film surface was not wettable with a non-polar organic solvent.
  • Non-polar solvent is commonly used for light emitting polymers and light-emitting small molecules.
  • the second portion of pH2 PAni/Nafion® was added with 0.1 M NaOH water solution to pH5.0. This portion of Na + containing dispersion was determined to contain 2.89% (w/w) PAni/Nafion®. Electrical conductivity of thin films made from the pH5.0 PAni/Nafion® was determined to be 3,8x10 -8 S/cm, which is also shown in Table 1.
  • PAni/Nafion® thin film was tested to be non-wettable with toluene. [Example 1]
  • This example illustrates effect of semiconductive nano-particles on enhancement of electrical conductivity and wettability of PAni/Nafion®, poly(tetrafluoroethylene)/ perfiuoroethersulfonic acid, films.
  • pH2 and pH5.0 PAni/Nafion® dispersions prepared in Comparative Example 1 were used to illustrate embodiments of this disclosure. 5.0166g pH2 PAni/Nafion® dispersion was added with 1.1313g
  • Celnax CX-Z300H-F2® (An aqueous zinc antimonite dispersion from Nissan Chemical Industries, Ltd. Houston, Texas, USA).
  • CX-Z300H-F2 has pH of about 7 and contains 26.47% (w/w) zinc antimonite particles, which are less than 20nm in size.
  • the weight ratio of PAni/Nafion® polymer to zinc antimonite in the formulation is about 0.47.
  • the mixture forms a stable dispersion with no sign of sedimentation of particles over a period at least five months. It also forms smooth, transparent films upon drying of water.
  • the data clearly illustrates that the particular tin antimonite particles from Celnax CX-Z300H-F2® are compatible with the PAni/
  • the process is to be improved by a more energy- intense process other than simply adding the two components together for improving surface smoothness having roughness less than at least 5nm.
  • Thin film conductivity of the dispersion containing PAni/Nafion® and zinc antimonite was determined to be 6.6x10 -4 S/cm (average of two film samples) at room temperature, which is also shown in Table 1. Conductivity was enhanced by more than four order magnitude. A piece of thin film was contacted with one drop of toluene. The toluene spread the film surface easily, which shows that the film becomes wettable with a common non-polar organic solvent. pH5.0 PAni/Nafion® was also added with CX-Z300H-F2 to determine its effect on conductivity and wettability. 5.0666g pH5.0
  • PAni/Nafion® dispersion was added with 1.1450g Celnax CX-Z300H-F2®.
  • the weight ratio of PAni/Nafion® polymer to zinc antimonite in the formulation is about 0.47.
  • the mixture forms a stable dispersion with no sign of sedimentation of particles. It also forms smooth, transparent films upon drying of water.
  • the data clearly illustrates that the particular tin antimonite particles from Celnax CX-Z300H-F2® are compatible with the
  • PAni/North® PAni/ National®.
  • the process is to be improved by a more energy-intense process other than simply adding the two components together for improving surface smoothness having roughness less than at least 5nm.
  • Thin film conductivity of the dispersion containing PAni/Nafion® and zinc antimonite was determined to be 9.3X10 -4 S/cm (average of two film samples) at room temperature, which is also shown in Table 1. Conductivity was enhanced by more than four order magnitude. A piece of thin film was contacted with one drop of toluene. The toluene spread the film surface easily, which shows that it becomes wettable with a common non-polar organic solvent.
  • This example illustrates preparation of an aqueous dispersion of polypyrrole (PPy) made in the presence of an aqueous dispersion of a copolymer of TFE (tetrafluoroethylene) and PSEPVE (perfluorinated 3,6- dioxa-4-methyl-7-octenesulfonic acid), a perfluorinated polymeric acid.
  • PPy polypyrrole
  • PSEPVE perfluorinated 3,6- dioxa-4-methyl-7-octenesulfonic acid
  • An aqueous dispersion of poly(TFE-PSEPVE) was prepared by heating poly(TFE-PSEPVE) having EW of 1000 in water to -270°C.
  • the aqueous poly(TFE-PSEPVE) dispersion had 25%(w/w) poly(TFE-PSEPVE) in water and was diluted to 10.8% with deionized water prior to the use for polymerization with pyrrole.
  • Pyrrole monomer was polymerized in the presence of the poly(TFE-PSEPVE) dispersion as described in published U.S. patent application 2005-0205860.
  • the aqueous PPy/poly(TFE-PSEPVE) dispersion was then pumped through three columns connected in series.
  • the three columns contain Dowex M-31 , Dowex M-43, and Dowex M-31 Na + , respectively.
  • the three Dowex ion-exchange resins are from Dow Chemicals Company, Midland, Michigan, USA.
  • the ion-resin treated dispersion was subsequently microfluidized with one pass at 5,000psi using a Microfluidizer Processor M-110Y (Microfluidics, Massachusetts, USA).
  • the microfluidized dispersion was then filtered and degassed to remove oxygen.
  • the pH of the dispersion was measured to be 4.0 using a standard pH meter and solid% was determined to be 6.4% by a gravimetric method. Films spin- coated from the dispersion and then baked at 130°C in air for 10 minutes has a conductivity of 7.5x10 -4 S/cm at room temperature.
  • the aqueous PPy/poly(TFE-PSEPVE) dispersion was first diluted from 6.4% to 3.12% before used for addition of silica nanoparticles.
  • the silica naoparticle dispersion used in this example is IPA(isopropanol)-ST-S from Nissan Chemical Company.
  • the IPA-ST-S contains 26w.% silica nanoparticle.
  • Particle size of the silica was measured with a Microtrac "nano-ultra" dynamic light scattering. It was found that 50 volume% of the silica had particle size of 7.1nm(nanometer) or less.
  • the silica dispersion was then mixed with a corresponding amount of PPy/poly(TFE-PSEPVE) dispersion to have desired silica w.% with respect to total solid, being PPy/poly(TFE-PSEPVE) and silica, which is listed in Table 2.
  • Table 2 The data clearly shows that contact angle of PPy/poly(TFE-PSEPVE) solid film formed by spin-coating drops drastically either with p-xylene or with anisole as silica is included.
  • This example illustrates the device performance of solution- processed organic light emitting diodes of a blue emitter using PPy/poly(TFE-PSEPVE) with and without silica as a buffer layer.
  • the ITO substrates were cleaned and treated in a UV-zone oven for 10 minutes before use.
  • Spin-coating of each PPy/poly(TFE-PSEPVE) dispersion with and without silica was set at conditions to provide thickness of 50nm after baked in air at 140°C for 7 minutes. They were then transferred to a dry box, in which all further top coating were conducted in an inert chamber.
  • the buffer layer was then top-coated with a 0.38% (w/v) toluene solution of HT-2, which is an arylamine-containing copolymer having hole transport properties, to achieve 20nm thickness after baked at 275°C for 30mins in argon.
  • HT-2 is an arylamine-containing copolymer having hole transport properties
  • the substrates were spin-coated with an emissive layer solution containing 13:1 fluorescent host: blue fluorescent dopant, and subsequently heated at 135°C for 15 minutes to remove solvent.
  • the layer thickness was approximately 40nm.
  • the substrates were then masked and placed in a vacuum chamber.
  • a 10nm thick layer of metal quinolate derivative as electron transporting layer was deposited by thermal evaporation, followed by a 0.8nm layer of cesium fluoride, and 100nm aluminum cathode layer.
  • the devices were encapsulated using a glass lid, getter pack, and UV curable epoxy.
  • the light emitting diode samples were characterized by measuring their (1 ) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage. All three measurements were performed at the same time and controlled by a computer.
  • the current efficiency (cd/A) of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device.
  • the power efficiency (LnVW) is the current efficiency divided by the operating voltage. The results are shown in Table 3, which illustrates that silica doesn't negatively affect device performance.

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Abstract

La présente invention concerne des compositions polymères électriquement conductrices et leur utilisation dans des dispositifs électroniques. Les compositions contiennent une dispersion aqueuse d’au moins un polymère électriquement conducteur dopé avec au moins un polymère d’acide très fluoré, et des nanoparticules inorganiques.
EP09800711.5A 2008-07-22 2009-02-25 Dispersions aqueuses de polymères électriquement conducteurs contenant des nanoparticules inorganiques Withdrawn EP2311047A4 (fr)

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PCT/US2008/070718 WO2009018009A1 (fr) 2007-07-27 2008-07-22 Dispersions aqueuses de polymères électriquement conducteurs contenant des nanoparticules minérales
PCT/US2009/035079 WO2010011368A1 (fr) 2008-07-22 2009-02-25 Dispersions aqueuses de polymères électriquement conducteurs contenant des nanoparticules inorganiques

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FR2964331B1 (fr) * 2010-09-03 2017-12-15 Commissariat Energie Atomique Membrane chimiquement stabilisee, son procede de preparation et ses utilisations
US9309370B2 (en) 2011-02-04 2016-04-12 3M Innovative Properties Company Amorphous perfluoropolymers comprising zirconium oxide nanoparticles
JP5655640B2 (ja) * 2011-03-08 2015-01-21 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子および有機エレクトロルミネッセンス素子の製造方法
CN103928636B (zh) * 2013-01-16 2016-06-22 国网山东省电力公司蓬莱市供电公司 一种有机电致发光器件的制备方法
CN103865263B (zh) * 2014-01-09 2016-05-11 常州大学 一种有机-无机复合红外隐身材料的制备方法
EP3002797B1 (fr) 2014-09-30 2020-04-29 Novaled GmbH Dispositif organique émetteur de lumière et affichage OLED actif
JP6312090B2 (ja) 2015-03-11 2018-04-18 信越化学工業株式会社 導電性材料及び基板
JP6294254B2 (ja) * 2015-03-23 2018-03-14 信越化学工業株式会社 導電性材料及び基板
JP6499535B2 (ja) * 2015-07-09 2019-04-10 信越化学工業株式会社 被覆品、及びパターン形成方法
JP6600286B2 (ja) * 2015-11-09 2019-10-30 信越化学工業株式会社 導電性材料及び基板
CN105968347B (zh) * 2016-05-23 2018-02-06 华东交通大学 N‑取代羧基聚苯胺/硫化镉量子点复合材料的制备方法
TWI618093B (zh) * 2016-12-14 2018-03-11 行政院原子能委員會核能研究所 具備高熱穩定性效能之有機太陽能電池之製備方法
EP3573117A4 (fr) * 2017-01-18 2020-10-28 Nissan Chemical Corporation Composition d'encre
CN113122070A (zh) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 组合物及其制备方法和发光二极管
CN113258009B (zh) * 2020-04-17 2022-08-05 广东聚华印刷显示技术有限公司 复合材料及其制备方法、量子点发光二极管

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JP2011529115A (ja) 2011-12-01
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