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
  • H01B1/06—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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • 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
  • H01B1/122—Ionic conductors
• • 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
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • 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
  • C08G2261/30—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • 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
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/70—Nanostructure
  • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less

Definitions

• This disclosure relates in general to aqueous dispersions of electrically conductive polymers containing additives, and their use in electronic devices.
• 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 hole injection layer in direct contact with an electrically conductive, inorganic oxide anode such as ITO.
• an aqueous dispersion comprising: (i) at least one electrically conductive polymer doped with at least one non-fluohnated polymeric acid; (ii) at least one highly-fluorinated acid polymer; and (iii) electrically insulative oxide nanoparticles.
• a film formed from the above dispersion there is provided a film formed from the above dispersion.
• electronic devices comprising at least one layer comprising the above film are provided.
• Figure 1 is a schematic diagram of an organic electronic device. Skilled artisans will appreciate that objects in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help to improve understanding of embodiments.
• an aqueous dispersion comprising: (i) at least one electrically conductive polymer doped with at least one non-fluohnated polymeric acid; (ii) at least one highly-fluorinated acid polymer; and (iii) electrically insulative oxide nanoparticles.
• the above dispersion is referred to herein as the "new composite dispersion".
• the new composite dispersion consists essentially of (i) at least one electrically conductive polymer doped with at least one non- fluorinated polymeric acid; (ii) at least one highly-fluorinated acid polymer; and (iii) electrically insulative oxide nanoparticles.
• 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.
• aqueous refers to a liquid that has a significant portion of water, and in one embodiment it is at least about 60% by weight water.
• conductive or “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.
• 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. In some embodiments, a conductor will form a layer having a conductivity of at least 10 "7 S/cm.
• doped as it refers to an electrically conductive polymer, is intended to mean that the electrically conductive polymer has a polymeric countehon 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.
• electrically insulative as it refers to oxide nanoparticles, is intended to mean that the addition of any amount of such nanoparticles to a composition or film does not increase the conductivity of such composition or film.
• 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.
• fluoro indicates that one or more available hydrogen atoms have been replaced with a fluorine atom.
• fluorine indicates that one or more available hydrogen atoms have been replaced with a fluorine atom.
• fluorine indicates that one or more available hydrogen atoms have been replaced with a fluorine atom.
• fluorine indicates that one or more available hydrogen atoms have been replaced with a fluorine atom.
• the terms “fully- fluorinated” and “perfluohnated” are used interchangeably and refer to a compound where all of the available hydrogens bonded to carbon have been replaced by fluorine.
• highly-fluorinated refers to a compound in which at least 80% of the available hydrogens bonded to carbon have been replaced by fluorine. Such materials are referred to as being at least 80% fluohnated.
• non-fluohnated refers to a compound in which less than 25% of the available hydrogens bonded to carbon have been replaced by fluorine. Such materials are referred to as being less than 25%
• 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.
• 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.
• Organic electronic device refers to a material having a particle size less than 50 nm at cumulative 50% volume distribution.
• 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
• polymer is intended to mean a material having at least one repeating monomehc 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.
• semiconductor is intended to refer to a material having characteristics of a semiconductor; that is having electrical conductivity greater than insulators but less than good conductors.
• wettable as it refers to a film, is intended to mean that an organic solvent will spread evenly across the surface of the film.
• work function is intended to mean the minimum energy needed to remove an electron from a conductive or semiconductive material to a point at infinite distance away from the surface.
• the work- function can be obtained by UPS (Ultraviolet Photoemission Spectroscopy), Kelvin-probe contact potential differential measurement, or low intensity X-ray photoemission spectroscopy (LIXPS). LIXPS was used exclusively in examples herein.
• light-emitting materials may also have some charge transport properties, the terms "hole transport layer, material, member, or structure” and “electron transport layer, material, member, or structure” are not intended to include a layer, material, member, or structure whose primary function is light emission.
• the doped electrically conductive polymer has a polymeric countehon derived from a non-fluorinated polymeric acid to balance the charge on the conductive polymer.
• any electrically conductive polymer can be used in the new composite dispersion.
• the electrically conductive polymer will form a film which has a conductivity in the range of 1x10 "3 to 1x10 "7 S/cm.
• the new composite dispersions described herein can be used to form films having a conductivity greater than about 1x10 ⁇ 7 S/cm, but greater than 1x10 "3 S/cm.
• the conductive polymers suitable for the new composite dispersion 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 composite dispersion 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(selenophenes), 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 composite dispersion 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
• 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 0 or an integer from 1 to 20 Z is H, alkali metal, alkaline earth metal, N(R 5 ) 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 Y 2 ) m -W- 1 where m is 2 or 3, W is O, S, Se, PO, 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 fluohnated. In some embodiments, all Y are hydrogen.
• the polymer is poly(3,4- ethylenedioxythiophene) ("PEDOT").
• PEDOT 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.
• At least one R 7 group is fluohnated. 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 composite dispersion 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, hydroxyl, 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, hydroxyl, 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. Unsubstituted polypyrrole is abbreviated herein as "PPy".
• 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 composite dispersion 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, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate
• the aniline monomehc unit can have Formula IV(a) or Formula IV(b) shown below, or a combination of both formulae.
• a is not O 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 composite dispersion have two or more fused aromatic rings, at least one of which is heteroaromatic.
• the fused polycyclic heteroaromatic monomer has Formula V:
• R 6 is hydrogen or alkyl
• R D 8 0 , D R9 s , R ,1'0 u , 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, 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
• 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), VG), and V(k):
• Q is S, Se, Te, or NH
• T is the same or different at each occurrence and is selected from
• 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 composite dispersion comprise Formula Vl:
• Q is S, Se, Te, 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.
• the copolymers are made by first forming an intermediate precursor monomer having the structure A-B-C, 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, Stille, 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 polyaniline, 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), unsubstituted polyaniline, unsubstituted polypyrrole, poly(4-aminoindole), poly(7-aminoindole), poly(thieno(2,3-b)thiophene), poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene).
• any non-fluorinated polymeric acid which is capable of doping the conductive polymer, can be used to make the new composite dispersions.
• the non-fluorinated polymeric acid is less than 10% fluorinated; in some embodiments, less than 1 % fluorinated. In some embodiments, the non-fluorinated polymeric acid has no fluorines.
• 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 acid is a non-fluorinated polymeric sulfonic acid.
• the acids are poly(styrenesulfonic acid) (“PSSA”), poly(2-acrylamido-2-methyl-1 -propanesulfonic acid) (“PAAMPSA”), and mixtures thereof.
• the amount of non-fluorinated polymeric acid present is generally in excess of that required to counterbalance the charge on the conducting polymer.
• the ratio of acid equivalents of non- fluorinated polymeric acid to molar equivalents of conducting polymer is in the range of 1 -5.
• the amount of doped conducting polymer in the new composite dispersion is generally at least 0.1 wt.%, based on the total weight of the dispersion. In some embodiments, the wt.% is from 0.2 to 5.
• the conductivity of films made from the doped polymer is in the range of 1 x10 "3 to 1 x10 "7 S/cm c.
• the doped electrically conductive polymer is formed by oxidative polymerization of the precursor monomer in the presence of the non- fluorinated polymeric acid in an aqueous medium. Oxidative polymerization of such monomers is well known. Oxidants such as sodium or potassium persulfate may be used. In some cases a catalyst, such as ferric sulfate can also be used. The resulting product is an aqueous dispersion of the doped electrically conductive polymer. Some doped electrically conductive polymers are available commercially. Examples include PEDOT/PSSA, sold as CleviosTM
• the highly-fluorinated acid polymer (“HFAP") is used to enhance the work-function of films made from the new composite dispersion.
• the HFAP 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 90% fluorinated; in some embodiments, at least 95% fluorinated; in some embodiments, fully- fluorinated.
• the HFAP is water-soluble.
• the HFAP is dispersible in water.
• the HFAP is organic solvent 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 -difluoro-2-(trifluoromethyl)allyloxy)-1 ,1 ,2,2-tetrafluoroethanesulfonic acid.
• the polymer is a copolymer of ethylene and 2- (2-(1 ,2,2-trifluorovinyloxy)-1 ,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: where:
• Rf is selected from highly-fluorinated alkylene, highly-fluorinated heteroalkylene, 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:
• 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.
• 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
• the HFAP comprises a perfluorocarbon backbone and the side chain represented by the formula -0-CF 2 CF(CFg)-O-CF 2 CF 2 SO 3 E 5 where E 5 is as defined above.
• HFAPs of this type are disclosed in U.S. Patent No.
• TFE tetrafluoroethylene
• PMMAF perfluoro(3,6-dioxa-4-methyl-7- octenesulfonyl fluoride)
• 4,358,545 and 4,940,525 has the side chain -0-CF 2 CF 2 SO 3 E 5 , wherein E 5 is as defined above.
• TFE tetrafluoroethylene
• POPF perfluoro(3-oxa-4-pentenesulfonyl fluoride)
• HFAP is available commercially as aqueous National® dispersions, from E. I. du Pont de Nemours and Company (Wilmington, DE).
• the ratio of acid equivalent of HFAP to acid equivalent of non-fluorinated doping acid is at least 0.1 , and no greater than 2; in some embodiments, no greater than 1.
• the HFAP can be dissolved or dispersed in the high-boiling solvent.
• the oxide nanoparticles are electrically insulative and have a particle size no greater than 50 nm at cumulative 50% volume distribution. In some embodiments, the particle size is no greater than 20 nm; in some embodiments, no greater than 10 nm; in some embodiments, no greater than 5 nm.
• the oxide can be either a single oxide or mixture of two or more oxides.
• the shape of the nanoparticles can be, fore example, spherical, elongated, chains, needles, core-shell nanoparticles, or combinations thereof.
• electrically insulative 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, tantalum oxides, and the like Combinations of two or more oxide nanoparticles can be used.
• the electrically insulative oxide nanoparticles are selected from the group consisting of silicon dioxide, titanium dioxide, and combinations thereof.
• the oxide nanoparticles can be made by the evaporation of the 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 multi-dimensional network oxides.
• the weight percentage of electrically insulative oxide nanoparticles in the new dispersion is in the range of 1 -20 wt.%, based on the total weight of the dispersion; in some embodiments, 5-10 wt%.
• the weight ratio of the electrically insulative oxide nanoparticles relative to the total of other solids (doped conducting polymer, HFAP, and optional additives) is at least 0.5; in some embodiments, at least 2.
• the weight ratio of electrically insulative oxide nanoparticles to conductive polymer is in the range of 0.5 to 10; in some embodiments, 2 to 5.
• the doped conductive polymer, HFAP, and electrically insulative oxide nanoparticles will be referred to in the singular. However, it is understood that more than one of any or all of these may be used.
• the new composite dispersion is prepared by first forming the doped conductive polymer and then adding the HFAP, the electrically insulative oxide nanoparticles, and optional additives in any order.
• the doped electrically conductive polymer is generally formed by oxidative polymerization of the precursor monomer in the presence of the non-fluorinated polymeric acid in an aqueous medium. Many of these materials are commercially available.
• the HFAP can be first dissolved or dispersed in the solvent or a solvent/water mixture.
• the electrically insulative oxide nanoparticles can similarly be dispersed in water or a solvent/water mixture. These mixtures can then be added to an aqueous dispersion of the doped conductive polymer.
• the electrically insulative oxide nanoparticles can also be dispersed with the HFAP or with the doped conductive polymer.
• the electrically insulative oxide nanoparticles can be added to the doped conductive polymer dispersion directly as a solid.
• the HFAP can be added to this mixture.
• the optional additive when present, can be added at any point.
• the additive can be added as a dispersion in water or a solvent/water mixture, or it can be added directly as a solid.
• the pH is increased either prior to or after the addition of the electrically insulative oxide nanoparticles and, optionally, the additive.
• the pH can be adjusted by treatment with cation exchange resins and/or base resins prior to the addition of the electrically insulative oxide nanoparticles and, optionally, the additive.
• 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.
• alkali metal is preferred over alkaline earth metal cations.
• Films made from the new composite aqueous dispersions 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.
• the films thus formed are smooth and relatively transparent. Films made from aqueous dispersions of electrically conductive polymers doped with at least one non-fluorinated polymeric acid often have low work function.
• the new films described herein are wettable with organic solvents.
• the new films are wettable by a non-polar organic solvent with a contact angle less than 50°.
• the new films are wettable by toluene or p-xylene with a contact angle no greater than 40°; in some embodiments, no greater than 35°.
• the new films are wettable by anisole with a contact angle no greater than 50°; in some embodiments, no greater than 45°.
• the methods for measuring contact angles are well known.
• the new films described herein have high work function. In some embodiments, the work function is greater than 5.3; in some embodiments, greater than 5.5.
• Low intensity X-ray photoemission spectroscope is a technique that has been demonstrated to be very useful in determining the work function of samples that are low in electrical conductivity or are sensitive to photon radiation, as described by Y. Yi, et. al., Journal of Applied Physics 100, 093719 (2006).
• this technique uses x rays of very low intensity (one order of magnitude lower than typical X-ray in XPS for elemental analysis, two to three orders of magnitude lower than commercial UV sources in UPS) to circumvent artifacts introduced by photoradiation, such as charging or photochemical reaction, allowing accurate measurement of work function.
• OLEDs are an organic electronic device comprising an organic layer capable of electroluminescence.
• OLEDs can have the following configuration:
• Electrodes having additional layers between the electrodes.
• Electrically conducting polymers having low conductivity in the range of 10 "3 to 10 ⁇ 7 S/cm are commonly used as the hole injection layer in direct contact with an electrically conductive, inorganic oxide anode such as ITO.
• hole injection layers deposited from the new composite dispersions.
• the term "hole injection layer” or “hole injection 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 new films described herein can be used in electronic devices where the high work function is desired in combination with transparency.
• the films are used as hole injection layers.
• Examples of electronic devices include, but are not limited to: (1 ) a device that converts electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, diode laser, or lighting panel), (2) a device that detects a signal using an electronic process (e.g., a photodetector, a photoconductive cell, a photoresistor, a photoswitch, a phototransistor, a phototube, an infrared (“IR”) detector, or a biosensors), (3) a device that converts radiation into electrical energy (e.g., a photovoltaic device or solar cell), (4) a device that includes one or more electronic components that include one or more organic semiconductor layers (e.g., a transistor or diode), (5) an electrolytic capacitor, or any combination of devices in items (1 ) through (5).
• a device that converts electrical energy into radiation e.g., a light-emitting diode, light emitting diode
• 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.
• FIG. 1 one embodiment of a device, 100, has an anode layer 110, an electroactive layer 140, and a cathode layer 160. Also shown the hole injection layer 120; an optional hole transport layer 130; and an optional electron injection/transport layer 150.
• the device may include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 160. Most frequently, the support is adjacent 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 160. Thus, the anode has a higher work-function than the cathode.
• 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 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. Examples of suitable materials include, but are not limited to, indium-tin-oxide (“ITO”). indium- zinc-oxide (“IZO”), aluminum-tin-oxide (“ATO”), aluminum-zinc-oxide (“AZO”), zirconium-tin-oxide (“ZTO”), gold, silver, copper, and nickel.
• ITO indium-tin-oxide
• IZO indium- zinc-oxide
• ATO aluminum-tin-oxide
• AZO aluminum-zin
• the mixed oxide layer is patterned.
• the pattern may vary as desired.
• the layer can be formed in a pattern by, for example, using a discontinuous deposition technique.
• the layer 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.
• Hole injection layer 120 comprises the new film described herein.
• the hole injection layer consists essentially of a film made from the aqueous composition described herein.
• optional hole transport layer 130 is present, between hole injection layer 120 and electroactive layer 140.
• hole transport materials for the hole transport layer 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 small molecules and polymers can be used.
• Commonly 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-methylphenyl)-[1 ,1'-biphenyl]-4,4'-diamine (TPD); 4, 4'- bis(carbazol-9-yl)biphenyl (CBP); 1 ,3-bis(carbazol-9-yl)benzene (mCP); 1 ,1 -bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC); N,N'-bis(4- methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1
• 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. In some cases, triarylamine polymers are used, especially triarylamine-fluorene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, published US patent application 2005-0184287 and published PCT application WO 2005/052027.
• the hole transport layer is doped with a p-dopant, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride.
• a p-dopant such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride.
• the electroactive layer 140 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, chrysenes, pyrenes, perylenes, rubrenes, coumarins, anthracenes, thiadiazoles, 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 iridium and platinum electroluminescent compounds, such as complexes of iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., U.S.
• the small molecule fluorescent or organometallic materials are deposited as a dopant with a host material to improve processing and/or electronic properties.
• conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymers thereof, and mixtures thereof.
• Optional electron transport layer 150 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 150 may promote electron mobility and reduce the likelihood of a quenching reaction if layers 140 and 160 would otherwise be in direct contact.
• Examples of electron transport materials which can be used in the optional electron transport layer 150 include metal chelated oxinoid compounds, including metal quinolate derivatives such as tris(8- hydroxyquinolato)aluminum (AIQ), bis(2-methyl-8-quinolinolato)(p- phenylphenolato) aluminum (BAIq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and 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-th(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline
• the cathode layer 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
• the cathode layer 160 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 cathode 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
• the cathode can be any metal or nonmetal having a lower work function than the anode.
• Materials for the cathode can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides.
• Li-containing organometallic compounds LiF, Li 2 O, Cs-containing organometallic compounds, CsF, Cs 2 O, and Cs 2 CO 3 can also be deposited between the organic layer and the cathode layer to lower the operating voltage. This layer may be referred to as an electron injection layer.
• the cathode layer 160 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 160 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 140.
• 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 injection layer 120, the hole transport layer 130, the electron transport layer 150, cathode layer 160, 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.
• the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000A; hole injection layer 120, 50-2000 A, in one embodiment 200-1000 A; optional hole transport layer 130, 50 -2000 A, in one embodiment 100- 1000 A; electroactive layer 140, 10-2000 A, in one embodiment 100-1000 A; optional electron transport layer 150, 50-2000 A, in one embodiment 100-1000 A; cathode 160, 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 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 called passive matrix OLED displays
• deposits of photoactive organic films may be excited by rows and columns of electrical contact layers.
• each dispersion sample was spread on a 3"x1 " microscope slide to cover 2/3 area of the slide. Excess of liquid was tilted to one edge of the slide to be soaked-up by a tissue. Once a smooth, homogeneous layer of liquid was ensured, the slide was placed on a flat surface for initial drying at room temperature. The slide was then placed on a hot plate set at 16O 0 C for 10 minutes. The whole operation was carried out in air. The film containing slide was removed from the hot plate and the film was trimmed to a long strip with a razor blade. Width of the strip ranged from 0.2cm to 0.7cm and the length was about 3cm.
• Silver paste was then painted perpendicular to the length of the strip to form four electrodes.
• the two inner parallel electrodes were about 0.3cm to 0.5 cm apart and were connected to a Keithley model 616 electrometer for measurement of voltage when a known current supplied by a Keithley model 225 Current Source was applied to the two other parallel electrodes.
• a series of corresponding current/voltage data obtained at room temperature was recorded to see whether Ohm's law was followed. All the samples in Examples and Comparative Examples followed Ohm's law, which provided a more or less identical resistance for the corresponding current/voltage data.
• the area in the two inner electrodes was measured for thickness with a Profilometer. Since resistance, thickness, separation length of the two inner electrodes and the width of the filmstrip are known, electrical conductivity is then calculated. The conductivity unit is expressed as S/cm (Siemens per centimeter).
• 1cmx1 cm ITO were first cleaned with water and isopropanol and then UV-ozned for 5 minutes before spin-coating of each sample described in comparative examples and examples. Three drops of each dispersion sample was applied on each ITO substrate and then taken to 4,000rpm in 08 seconds on a spin-coater, and remained at the speed for one minute. The coated samples were then baked in air at 14O 0 C for 7 minutes. Samples cooled down in air before being loaded one at a time into the chamber for Low Intensity X-ray Photoemission Spectroscopy (LIXPS). The sample is mounted on a titanium sample holder in a laminar flow hood (in air).
• LIXPS Low Intensity X-ray Photoemission Spectroscopy
• Nanoparticle dispersed in a liquid was measured at various concentrations using Microtrac Nanotrac based on dynamic light scattering technique.
• the particle size is summarized in cumulative % of volume distribution.
• This comparative example illustrates the preparation and properties of a conductive polymer doped with a non-fluorinated polymeric acid and blended with a perfluorinated acid polymer.
• Baytron-P ® AI4083 is an aqueous dispersion of PEDOT-PSSA from H. C. Starck GmbH (Leverkuson, Germany).
• PEDOT/PSSA is an abbreviation for poly (3,4-ethylene-dioxythiophene) doped with poly (styrenesulfonic acid), a nonfluorinated polymeric acid.
• the weight ratio of PEDOT to PSSA of the Baytron-P ® is 1 :6.
• the work function was measured to be 5.33eV. Electrical conductivity of thin films was measured to be 1.7x10 ⁇ 4 S/cm, and 7.9x10 ⁇ 4 S/cm at room temperature.
• the HFAP was a copolymer of tetrafluoroethylene (TFE) and perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid (PSEPVE), referred to as p-(TFE-PSEPVE).
• TFE tetrafluoroethylene
• PSEPVE perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid
• the p-(TFE-PSEPVE) used for the blending was an aqueous colloidal dispersion having an acid equivalent (EW) of 1000.
• EW means weight in gram of the polymer per one sulfonic acid group.
• a 25% (w/w) dispersion of p-(TFE-PSEPVE) in water was made using a procedure similar to the procedure in US Patent 6,150,426, Example 1 , Part 2, except that the temperature was approximately 27O 0 C.
• the dispersion was diluted with water to form a10.93% (w/w) dispersion for further use.
• This example illustrates the properties of an aqueous dispersion of a conductive polymer doped with a non-fluorinated polymeric acid, a highly-fluorinated acid polymer, and electrically insulative oxide nanoparticles.
• the PEDOT-PSSA/TFE-PSEPVE copolymer dispersion prepared in Comparative Example A were added with 0.384Og of 21.2% (w/w) silica in ethylene glycol.
• the silica in ethylene glycol is marketed as EG-ST by Nissan Chemical Company in Houston, Texas.
• the PEDOT- PSSA/TFE-PSEPVE copolymer/silica dispersion contain 5.31 w% total solid wherein 2.83% is silica and the rest, 2.48%, is PEDOT-PSSA/p-(TFE- PSEPVE).
• the wt.% of silica with respect to total solids is 53.3%.
• the ethylene glycol present from the EG-ST is 10.5 wt.%, based on the total weight of the dispersion.
• a couple drops of the PEDOT-PSSA/p-(TFE-PSEPVE)/silica dispersion were made into thin films and the work function was determined to be 5.72eV which drops only 0.24eV with the silica, as compared to the material in Comparative Example A, but is still very high for OLED applications as a hole injection layer.
• its contact angle with p- xylene dropped from 48.5° to 29° with p-xylene.
• the drop of the contact angle is quite substantial, which means the film surface is very wettable with the organic solvent.
• the silica dispersion in ethylene glycol has a particle size of about
• Table 1 shows particle size of the silica dispersion in ethylene glycol at three concentrations. It has a particle size of about 3.9 nanometers (nm) at cumulative 50% volume distribution.
• This comparative example illustrates the properties of an aqueous dispersion of a conductive polymer doped with a non-fluorinated polymeric acid blended with a highly-fluorinated acid polymer, where the HFAP is present in a higher concentration than in Comparative Example A.
• PEDOT/PSSA and p-(TFE-PSEPVE) were used. 2.7817g of the p-(TFE-PSEPVE) was slowly added to 10.0137g Baytron-P ® AI4083. The resulting dispersion contained 3.66%(w/w) solid in which the equivalent acid ratio between p-(TFE- PSEPVE) polymer and PSSA is 0.4.
• a couple drops of the PEDOT-PSSA/ p-(TFE-PSEPVE) dispersion were made into thin films and the work function was determined to be 6.07eV, which is high and effective for OLED applications as a hole injection layer. However the contact angle with p-xylene was 48.5° and with anisole was 55.8°. These contact angles are very high and the film surface is not wettable with the organic solvents.
• Example 2 This example illustrates the properties of an aqueous dispersion of a conductive polymer doped with a non-fluorinated polymeric acid, a highly- fluorinated acid polymer, and electrically insulative oxide nanoparticles.
• PEDOT-PSSA/TFE-PSEPVE copolymer dispersion prepared in comparative example 2 were added with 1.3784g of 21.2% (w/w) silica in ethylene glycol.
• the PEDOT-PSSA/TFE-PSEPVE copolymer/silica dispersion contain 8.16w% total solid wherein 5.43% is silica and the rest, 2.73%, is PEDOT-PSSA/p(TFE-PSEPVE).
• the w.% of silica with respect to total solid is 66.5%.
• the ethylene glycol present from the EG-ST is 20.2 wt.%, based on the total weight of the dispersion.
• a couple drops of the PEDOT-PSSA/p-(TFE-PSEPVE)/silica dispersion were made into thin films and work-function was determined to be 5.81 eV which drops only 0.26eV with the silica, but still very high for OLED application as a hole injection layer.
• the electrical conductivity of thin films cast from the silica containing dispersion was measured to be 1.7x10 ⁇ 4 S/cm, and 9.3x10 ⁇ 5 S/cm at room temperature.
• the conductivity is similar to the conductivity of Baytron-P ® AI4083.
• the data shows that addition of silica and ethylene glycol do not affect the electrical conductivity.
• Silica wt% is based on total solids; acid equiv. ratio is acid equivalent ratio of p-(TFE- PSEPVE) to PSSA; Wf is work function; CA is contact angle, in degrees.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Nanotechnology (AREA)
• General Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Composite Materials (AREA)
• Dispersion Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Electroluminescent Light Sources (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Conductive Materials (AREA)
• Electrodes Of Semiconductors (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (2)

Family

ID=43011760

Family Applications (1)

Country Status (7)

Cited By (3)

Families Citing this family (14)

Family Cites Families (174)

• 2010
  • 2010-04-23 KR KR1020117027924A patent/KR101581991B1/ko active Active
  • 2010-04-23 CN CN201080017846.6A patent/CN102395627B/zh active Active
  • 2010-04-23 JP JP2012507410A patent/JP2012524834A/ja active Pending
  • 2010-04-23 US US13/265,002 patent/US8945427B2/en active Active
  • 2010-04-23 EP EP10767815.3A patent/EP2421919A4/en not_active Withdrawn
  • 2010-04-23 WO PCT/US2010/032175 patent/WO2010124166A2/en not_active Ceased
  • 2010-04-23 TW TW99112912A patent/TW201100482A/zh unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events