WO2016090087A1

WO2016090087A1 - Electrically conductive polymer films and complexes containing a conductivity enhancing agent, and electronic devices containing such films and complexes

Info

Publication number: WO2016090087A1
Application number: PCT/US2015/063626
Authority: WO
Inventors: Chantal Badre; Bastien LABLANCHY; Lawrence Alan Hough
Original assignee: Rhodia Operations
Priority date: 2014-12-05
Filing date: 2015-12-03
Publication date: 2016-06-09

Abstract

Described herein are polymer films and polymer complexes, including polymer gels and polymer foams, containing electrically conductive polymers and at least one conductivity enhancing agent. The polymer films and polymer complexes described herein are useful as components of electronic devices.

Description

ELECTRICALLY CONDUCTIVE POLYMER FILMS AND COMPLEXES CONTAINING A CONDUCTIVITY ENHANCING AGENT, AND ELECTRONIC

DEVICES CONTAIN ING SUCH FILMS AND COMPLEXES

Cross Reference to Related Applications

[0001 ] This application claims the priority of U.S. Provisional Application No. 62/087,856, filed December 5, 2014. The entire content of this application is explicitly incorporated herein by this reference.

Field of the Invention

[0002] The present invention relates to polymer films and polymer complexes comprising electrically conductive polymers and at least one conductivity enhancing agent, and electronic devices containing such films and complexes.

Background

[0003] High electrical conductivity is a desirable feature in various electronic devices, including, for example, energy storage devices, transistors, photovoltaic devices, display devices, and the like. Electrical conductivity can be achieved by application of a thin metallic coating such as gold, silver or copper, or a metal oxide coating containing Indium Tin Oxide (ITO) to a substrate. Transparent conductive oxide films such as ITO are used in a wide variety of applications such as, but not limited to, LCDs, OLEDs, solar cells, and the like. ITO films tend to have weak mechanical strength and low flexibility, which makes them fragile and readily damaged during bending. In addition, ITO films are generally applied using vacuum deposition and are therefore not amenable to wet processing. There is a variety of technical approaches for developing ITO substitutes and there are four areas in which these various alternatives compete: price, electrical conductivity, optical transparency, and physical resiliency. [0004] Electrically conductive polymers, such as polythiophene polymers, particularly a polymer blend of poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) ("PEDOT-PSS"), have been investigated as possible alternatives to metallic coatings, particularly ITO coatings, for use in various applications requiring high electrical conductivity. The electrical conductivity of electrically conductive polymers is typically lower than that of ITO, but can be enhanced through the use of conductive fillers, such as carbon nanotubes, and dopants. However, the performance of such materials still falls short of that of ITO and trade-offs exist between optimizing the electrical conductivity and optimizing the price, optical transparency, and physical resiliency of components comprising electrically conductive polymers.

[0005] There is an ongoing unresolved interest in increasing the electrical conductivity of electrically conductive polymers, more specifically of PEDOT-PSS.

Summary of the Invention

[0006] In a first aspect, the present invention is directed to a polymer film or polymer complex comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants, and

(c) at least one conductivity enhancing agent described herein.

[0007] In a second aspect, the present invention is directed to a process for producing a polymer film described herein, the process comprising:

(1 a) treating a pristine polymer film with at least one conductivity enhancing agent described herein, or a solution thereof; (2a) optionally washing the polymer film obtained in step (1 a), thereby producing the polymer film.

[0008] In a third aspect, the present invention is directed to a polymer

composition comprising: (a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants,

(c) at least one conductivity enhancing agent described herein, and

(d) a liquid medium.

[0009] In a fourth aspect, the present invention is directed to a process for producing a polymer film, the process comprising:

(1 b) forming a layer of a polymer composition described herein,

(2b) removing the liquid medium from the layer,

thereby producing the polymer film.

[00010] In a fifth aspect, the present invention is directed to a process for producing a polymer complex described herein, the process comprising:

(1 c) treating a pristine polymer complex with at least one conductivity enhancing agent described herein, or a solution thereof, (2c) optionally washing the polymer complex obtained in step (1 c), thereby producing the polymer complex.

[0001 1 ] In a sixth aspect, the present invention is directed to an electronic device, comprising:

(a) an anode layer,

(b) a cathode layer,

(c) an electroactive layer disposed between the anode layer and the cathode layer,

(d) optionally, a buffer layer or hole injection layer,

(e) optionally, a hole transport layer, and

(f) optionally, an electron injection layer,

wherein at least one of the layers comprises a polymer film or polymer complex described herein.

Brief Description of the Drawings [00012] FIG. 1 shows a schematic diagram of an electronic device described herein.

Detailed Description of the Invention

[00013] As used herein, the terms "a", "an", or "the" means "one or more" or "at least one" unless otherwise stated.

[00014] As used herein, the term "comprises" includes "consists essentially of and "consists of. The term "comprising" includes "consisting essentially of and "consisting of.

[00015] As used herein, the following terms have the meanings ascribed below:

"acidic group" means a group capable of ionizing to donate a hydrogen ion, "anode" means an electrode that is more efficient for injecting holes compared to a given cathode,

"buffer layer" generically refers to electrically conductive or semiconductive materials or structures that have one or more functions in an electronic device, including but not limited to, planarization of an adjacent structure in the device, such as an 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 electronic device,

"cathode" means an electrode that is particularly efficient for injecting electrons or negative charge carriers,

"confinement layer" means a layer that discourages or prevents quenching reactions at layer interfaces,

"doped" as used herein in reference to an electrically conductive polymer means that the electrically conductive polymer has been combined with a compound that alters the properties of the electrically conductive polymer, which properties may include, but may not be limited to, electrical properties, such as work function, mechanical properties, and optical properties. Such a compound is referred to herein as a "dopant", and is typically a polymer acid, which is referred to herein as a "polymer acid dopant",

"doped electrically conductive polymer" means a polymer blend comprising an electrically conductive polymer and a dopant, typically a polymer acid dopant, for the electrically conductive polymer,

"electrically conductive polymer" means any polymer or polymer blend that is inherently or intrinsically, without the addition of electrically conductive fillers such as carbon black or conductive metal particles, capable of electrical conductivity, more typically to any polymer or oligomer that exhibits a bulk specific conductance of greater than or equal to 10^"7 Siemens per centimeter ("S/cm"), unless otherwise indicated, a reference herein to an "electrically conductive polymer" include any optional polymer acid dopant,

"electrically conductive" includes conductive and semi-conductive,

"electroactive" when used herein in reference to a material or structure, means that the material or structure exhibits properties that respond to the movement of ions, electrons, and/or holes, such as emitting radiation, facilitating redox reactions to store electrical energy, changing in optical characteristics, such as color, etc.; or properties that generate or change the movement of ions, electrons and/or holes as response to external stimulus, such as exhibiting a change in electrical conductivity upon mechanical perturbation, facilitating redox reactions to provide electrical energy, producing electrical energy in the presence of a

temperature gradient, or exhibiting a change in concentration of electron-hole pairs when receiving radiation;

"electronic device" means a device that comprises one or more layers comprising one or more semiconductor materials and makes use of the controlled motion of electrons through the one or more layers,

"electron injection/transport", as used herein in reference to a material or structure, means that such material or structure that promotes or facilitates migration of negative charges through such material or structure into another material or structure,

"high-boiling solvent" refers to an organic compound which is a liquid at room temperature and has a boiling point of greater than 100°C, "hole injection/transport" when used herein when referring to a material or structure, means such material or structure facilitates migration of positive charges through the thickness of such material or structure with relative efficiency and small loss of charge,

"layer" as used herein in reference to an electronic device, means a coating covering a desired area of the device, wherein the area is not limited by size, that is, the area covered by the layer can, for example, be as large as an entire device, be as large as a specific functional area of the device, such as the actual visual display, or be as small as a single sub-pixel,

"polymer" includes homopolymers and copolymers, and

"polymer blend" means a blend of two or more polymers.

[00016] As used herein, the term "polymer complex" refers to one or more polymers optionally in combination with one or more non-polymeric materials wherein the one or more polymers and the optional one or more non-polymeric materials are interconnected by means other than covalent bonds (such as, for example, physical entanglements, hydrogen bonds, or ionic bonds) or by both covalent bonds and by means other than covalent bonds. Polymer complexes include, but are not limited to, polymer gels, polymer foams, and the like.

[00017] As used herein, the term "polymer gel", "gel" or "gel material" refers to a polymer complex that is characterized as a solid and a continuous liquid phase.

[00018] As used herein, the term "polymer foam", "foam", or "foam material" refers to a polymer complex that is characterized as a solid and a continuous gas phase.

[00019] As used herein, the term "pristine" in reference to a polymer film or polymer complex means that the polymer film or polymer complex is free of conductivity enhancing agent, as defined herein. The phrase "free of means that there is no external addition of the material denoted by the term modified and that there is no detectable amount of the material denoted by the term modified. Thus, for example, the term "free of conductivity enhancing agent" means that there is no external addition of conductivity enhancing agent and that there is no detectable amount of conductivity enhancing agent that may be observed by analytical techniques known to the ordinarily-skilled artisan, such as, for example, gas or liquid chromatography, spectrophotometry, optical microscopy, and the like.

[00020] As used herein, the terminology "(C_x-C_y)" in reference to an organic group, wherein x and y are each integers, means that the group may contain from x carbon atoms to y carbon atoms per group.

[00021 ] As used herein, the term "alkane" means a straight or branched saturated hydrocarbon, more typically, a straight or branched saturated (d- C ₀)hydrocarbon, such as, for example, methane, ethane, n-propane, isopropane, n- butane, isobutane, tert-butane, hexane, octane, hexadecane, octadecane, eicosane, and tetracontane.

[00022] As used herein, the term "cycloalkane" means a saturated

hydrocarbon, more typically a saturated (C3-C22) hydrocarbon, in which the carbon atoms form one or more rings. When a cycloalkane contains more than one ring, adjacent rings may be linked to each other by one or more bonds or divalent bridging groups or may be fused together. Examples of cycloalkanes include, but are not limited to, norbornane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and decalin.

[00023] The term "cycloalkene" refers to a cycloalkane in which one or more carbon-carbon single bonds are each replaced with a carbon-carbon double bond. Examples of cycloalkenes include, but are not limited to, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene and cyclooctadiene.

[00024] The term "cyclic ether" refers to a cycloalkane or cycloalkene in which one or more carbon atoms are each replaced with an oxygen atom. Cyclic ethers include, but are not limited to, tetrahydrofuran, pyran, tetrahydropyran, dioxane, oxocane, and crown ethers.

[00025] The term "cyclic ester" refers to a cycloalkane or cycloalkene in which one or more carbon atoms are each replaced with a -C(0)0- group. Cyclic esters include, but are not limited to, butyrolactone, furanone, valerolactone, and caprolactone.

[00026] As used herein, the term "arene" refers to a compound having one or more unsaturated six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds. Arenes may be monocyclic or polycyclic. Monocyclic arenes refer to compounds having one unsaturated six- membered carbon ring in which the unsaturation may be represented by three conjugated double bonds. An example of monocyclic arenes is benzene. Polycyclic arenes refer to compounds having more than one unsaturated six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, wherein adjacent rings may be linked to each other by one or more bonds or divalent bridging groups or may be fused together. Examples of polycyclic arenes include, but are not limited to, anthracene, naphthylene, phenanthrene, fluorene, and pyrene.

[00027] As used herein, the term "heteroarene" means an arene in which one or more of the carbon atoms are each replaced by a heteroatom, such as, for example, nitrogen, oxygen, and sulfur. Heteroarenes also include arenes in which two adjacent carbon atoms are replaced by one heteroatom. Examples of heteroarenes include, but are not limited to, furan, thiophene, pyrrole, pyridine, pyrimidine, pyrazine, triazine, pyridazine, tetrazole, imidazole, indole, and quinolone.

[00028] Any alkane, cycloalkane, cycloalkene, cyclic ether, cyclic ester, arene, and heteroarene, may optionally be substituted at one or more carbon atoms with one or more substituents, which may be same or different, described herein. [00029] As used herein, the term "halo" means a halogen or halide radical and includes, for example, fluoride (F), chloride (CI), bromide (Br), iodide (I), and astatide (At).

[00030] As used herein, the term "hydroxy" refers to the -OH radical.

[00031 ] As used herein, the term "carboxy" refers to the -C(0)OH radical.

[00032] As used herein, the term "sulfonic acid" refers to the -S(0)₂OH radical.

[00033] As used herein, the term "alkyl" means a monovalent straight or branched saturated hydrocarbon radical, more typically, a monovalent straight or branched saturated (CrC ₀)hydrocarbon radical, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, tricontyl, and tetracontyl.

[00034] As used herein, the term "cycloalkyl" means a saturated hydrocarbon radical, more typically a saturated (C3-C22) hydrocarbon radical, in which the carbon atoms form one or more rings, such as, for example, cyclopropyl, cyclopentyl, cycloheptyl, and cyclooctyl.

[00035] The term "heteroalkyl" means an alkyl group wherein one or more of the carbon atoms within the alkyl group has been replaced by a heteroatom, such as, for example, nitrogen, oxygen, or sulfur.

[00036] The term "haloalkyl" means an alkyl radical, more typically a (d- C22)alkyl radical, that is substituted with one or more halogen atoms, such as fluorine, chlorine, bromine, and iodine. Examples of haloalkyl groups include, for example, trifluoromethyl, 1 H,1 H,2H,2H-perfluorooctyl, perfluoroethyl.

[00037] As used herein, the term "hydroxyalkyl" means an alkyl radical, more typically a (Ci-C22)alkyl radical, that is substituted with one or more hydroxy groups, including, for example, hydroxymethyl, hydroxyethyl, dihydroxyethyl, for example, - CH(OH)CH₂OH, hydroxypropyl, and hydroxydecyl.

[00038] As used herein, the term "carboxyalkyl" means an alkyl radical, more typically a (CrC₂2)alkyl radical, that is substituted with one or more carboxy groups, including, for example, carboxymethyl, carboxyethyl, and carboxypropyl.

[00039] As used herein, the term "alkoxy" refers to a monovalent radical having the structure represented by "alkyl-O", more typically, by "(C C₂2)alkyl-0-".

Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, and tert-butoxy.

[00040] As used herein, the term "alkoxyalkyl" means an alkyl radical that is substituted with one or more alkoxy substituents, more typically a (Ci-C₂₂)alkoxy-(Ci- Ce)alkyl radical, including, for example, methoxymethyl, ethoxyethyl, and

ethoxybutyl.

[00041 ] As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds. Aryl radicals include monocyclic aryl and polycyclic aryl. Polycyclic aryl refers to a monovalent unsaturated hydrocarbon radical containing more than one six-membered carbon ring in which the unsaturation may be represented by three conjugated double bonds wherein adjacent rings may be linked to each other by one or more bonds or divalent bridging groups or may be fused together. Examples of aryl radicals include, but are not limited to, phenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, and pyrenyl.

[00042] As used herein, the term "carboxyaryl" means an aryl radical that is substituted with one or more carboxy groups, including, for example, carboxyphenyl, dicarboxyphenyl, and carboxynaphthyl. [00043] As used herein, the term "aroyl" refers to a monovalent radical having the structure represented by "aryl-C(O)-". Examples of aroyl groups include, but are not limited to, benzoyl, methylbenzoyl, and ethylbenzoyl.

[00044] As used herein, the term "alkenyl" means an unsaturated straight or branched hydrocarbon radical, more typically an unsaturated straight, branched, (C₂- C22) hydrocarbon radical, that contains one or more carbon-carbon double bonds, including, for example, ethenyl (vinyl), n-propenyl, and iso-propenyl, and allyl.

[00045] As used herein, the term "cycloalkenyl" means an unsaturated hydrocarbon radical, typically an unsaturated (C3-C22) hydrocarbon radical, that contains one or more cyclic alkenyl rings and which may optionally be substituted on one or more carbon atoms of the ring with one or two (Ci-C6)alkyl groups per carbon atom, including, for example, cyclohexenyl and cycloheptenyl.

[00046] As used herein, the term "alkynyl" means an unsaturated straight or branched hydrocarbon radical, more typically an unsaturated straight, branched, (C2- C22) hydrocarbon radical, that contains one or more carbon-carbon triple bonds, including, for example, ethynyl, propynyl, and butynyl.

[00047] As used herein, the term "arylalkyl" means an alkyl group substituted with one or more aryl groups, more typically a (CrCi8)alkyl substituted with one or more aryl substituents, including, for example, phenylmethyl (benzyl), phenylethyl, and triphenylmethyl.

[00048] Any substituent described herein may optionally be substituted at one or more carbon atoms with one or more, same or different, substituents described herein.

[00049] As used herein, the following terms refer to the corresponding substituent groups:

"amido" is -R¹-C(0)N(R⁶)R⁶, "amidosulfonate" is -R¹-C(0)N(R⁴)R²-S0₃Z,

"benzyl" is -CH₂-C₆H₅,

"carboxylate" is -R¹-C(0)0-Z or -R¹-0-C(0)-Z,

"ether" is -R¹-(0-R³)_p-0-R³,

"ether carboxylate" is -R¹-0-R²-C(0)0-Z or -R¹-0-R²-0-C(0)-Z,

"ether sulfonate" is -R¹-0-R²-S0₃Z,

"ester sulfonate" is -R¹-0-C(0)R²-S0₃Z, and

"urethane" is -R¹-0-C(0)-N(R⁴)₂,

wherein:

each R¹ is absent or alkylene,

each R² is alkylene,

each R³ is alkyl,

each R⁴ is H or an alkyl,

p is 0 or an integer from 1 to 20, and

each Z is H, alkali metal, alkaline earth metal, N(R³)₄ or R³,

wherein any of the above groups may be non-substituted or substituted, and any group may have fluorine substituted for one or more hydrogens, including

perfluorinated groups.

[00050] The present invention relates to a polymer film or polymer complex comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants, and

(c) at least one conductivity enhancing agent.

[00051 ] The electrically conductive polymer described herein may comprise one or more homopolymers, one or more co-polymers of two or more respective monomers, or a mixture of one or more homopolymers and one or more copolymers. The respective electrically conductive polymer may each comprise a single polymer or may comprise a blend two or more polymers which differ from each other in some respect, for example, in respect to composition, structure, or molecular weight. [00052] In an embodiment, the electrically conductive polymer comprises one or more electrically conductive polymers selected from electrically conductive polythiophene polymers, electrically conductive poly(selenophene) polymers, electrically conductive poly(telurophene) polymers, electrically conductive polypyrrole polymers, electrically conductive polyaniline polymers, electrically conductive fused polycylic heteroaromatic polymers, and blends of any such polymers.

[00053] In one embodiment, the electrically conductive polymer comprises one or more polymers selected from electrically conductive polythiophene polymers, electrically conductive poly(selenophene) polymers, electrically conductive poly(telurophene) polymers, and mixtures thereof Suitable polythiophene polymers, poly(selenophene) polymers, poly(telurophene) polymers and methods for making such polymers are generally known. In one embodiment, the electrically conductive polymer comprises at least one electrically conductive polythiophene polymer, electrically conductive poly(selenophene) polymer, or electrically conductive poly(telurophene) polymer that comprises 2 or more, more typically 4 or more, monomeric units according to structure (I) per molecule of the polymer:

wherein:

Q is S, SE, or Te, and

each occurrence of R¹¹ and each occurrence of R¹² is independently H, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, 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, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane, or both the R¹¹ group and R¹² group of a given monomeric unit are fused to form, together with the carbon atoms to which they are attached, an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, selenium, tellurium, sulfur, or oxygen atoms.

[00054] In one embodiment, Q is S, the R¹¹ and R¹² of the monomeric unit according to structure (I) are fused and the electrically conductive polymer comprises a polydioxythiopene polymer that comprises 2 or more, more typically 4 or more, monomeric units according to structure (I. a) per molecule of the polymer:

wherein:

each occurrence of R¹³ is independently H, alkyl, hydroxy, heteroalkyl, alkenyl, heteroalkenyl, hydroxyalkyl, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, or urethane, and

m' is 2 or 3.

[00055] In one embodiment, all R¹³ groups of the monomeric unit according to structure (I. a) are each H, alkyl, or alkenyl. In one embodiment, R¹³ groups of the monomeric unit according to structure (I. a) are not each H. In one embodiment, each R¹³ groups of the monomeric unit according to structure (I. a) is H.

[00056] In one embodiment, the electrically conductive polymer comprises an electrically conductive polythiophene homopolymer of monomeric units according to structure (I. a) wherein each R¹³ is H and m' is 2, known as poly(3,4- ethylenedioxythiophene), more typically referred to as "PEDOT". [00057] In one embodiment, the electrically conductive polymer comprises one or more electrically conductive polypyrrole polymers. Suitable electrically conductive polypyrrole polymers and methods for making such polymers are generally known. In one embodiment, the electrically conductive polymer comprises a polypyrrole polymer that comprises 2 or more, more typically 4 or more, monomeric units according to structure (II) per molecule of the polymer:

wherein:

each occurrence of R²¹ and each occurrence of R²² is independently H, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, 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, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, or the R²¹ and R²² of a given pyrrole unit are fused to form, together with the carbon atoms to which they are attached, an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms, and each occurrence of R²³ is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane

[00058] In one embodiment, each occurrence of R²¹ and each occurrence of R²² is independently H, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, urethane, epoxy, silane, siloxane, or alkyl, wherein the alky group may optionally be substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxy, epoxy, silane, or siloxane moieties.

[00059] In one embodiment, each occurrence of R²³ is independently H, alkyl, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxy, epoxy, silane, or siloxane moieties.

[00060] In one embodiment, each occurrence of R²¹, R²², and R²³ is H.

[00061 ] In one embodiment, R²¹ and R²² are fused to form, together with the carbon atoms to which they are attached, a 6- or 7-membered alicyclic ring, which is further substituted with a group selected from alkyl, heteroalkyl, hydroxy,

hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. In one embodiment, and R²² are fused to form, together with the carbon atoms to which they are attached, a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group. In one embodiment, R²¹ and R²² are fused to form, together with the carbon atoms to which they are attached, a 6- or 7- membered alicyclic ring, which is further substituted with an alkyl group having at least 1 carbon atom.

[00062] In one embodiment, R²¹ and R²² are fused to form, together with the carbon atoms to which they are attached, a -0-(CHR²⁴)n'-0- group, wherein:

each occurrence of R²⁴ is independently H, alkyl, hydroxy, hydroxyalkyl, benzyl, carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, and

n' is 2 or 3. [00063] In one embodiment, at least one R group is not hydrogen. In one embodiment, at least one R²⁴ group is a substituent having F substituted for at least one hydrogen. In one embodiment, at least one Y group is perfluorinated.

[00064] In one embodiment, the electrically conductive polymer comprises one or more electrically conductive polyaniline polymers. Suitable electrically conductive polyaniline polymers and methods of making such polymers are generally known. In one embodiment, the electrically conductive polymer comprises a polyaniline polymer that comprises 2 or more, more typically 4 or more, monomeric units selected from monomeric units according to structure (III) and monomeric units according to structure (Ill.a) per molecule of the polymer:

wherein:

each occurrence of R³¹ and R³² s independently alkyl, alkenyl, alkoxy, cycloalkyi, cycloalkenyl, alkanoyi, alkylthio, aryloxy, alkylthioalkyi, alkylaryl, arylalkyi, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyi, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more of sulfonic acid, carboxylic acid, halo, nitro, cyano or epoxy moieties, or two R³¹ or R³² groups on the same ring may be fused to form, together with the carbon atoms to which they are attached, a 3, 4, 5, 6, or 7- membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms; and

each a and a' is independently an integer from 0 to 4,

each b and b' is integer of from 1 to 4, wherein, for each ring, the sum of the a and b coefficients of the ring or the a' and b' coefficients of the ring is 4.

[00065] In one embodiment, a or a' = 0 and the polyaniline polymer is an non- substituted polyaniline polymers referred to herein as a "PAN I" polymer.

[00066] In one embodiment, the electrically conductive polymer comprises one or more electrically conductive polycylic heteroaromatic polymers. Suitable electrically conductive polycylic heteroaromatic polymers and methods for making such polymers are generally known. In one embodiment, the electrically conductive polymer comprises one or more polycylic heteroaromatic polymers that comprise 2 or more, more typically 4 or more, monomeric units per molecule that are derived from one or more heteroaromatic monomers, each of which is independently according to Formula (IV):

(IV) wherein:

Q is S or NH,

R⁴¹, R⁴², R⁴³, and R⁴⁴ are each independently H, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, 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, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, or urethane, provided that at least one pair of adjacent substituents R⁴¹ and R⁴², R⁴² and R⁴³, or R⁴³ and R⁴⁴ are fused to form, together with the carbon atoms to which they are attached, a 5 or 6-membered aromatic ring, which ring may optionally include one or more hetero atoms, more typically selected from divalent nitrogen, sulfur and oxygen atoms, as ring members.

[00067] In one embodiment, the polycylic heteroaromatic polymers comprise 2 or more, more typically 4 or more, monomeric units per molecule that are derived from one or more heteroaromatic monomers, each of which is independently according to structure (V):

wherein:

Q is S, Se, Te, or NR⁵⁵,

T is S, Se, Te, NR⁵⁵, O, Si(R⁵⁵)₂, or PR⁵⁵,

E is alkenylene, arylene, and heteroarylene,

R⁵⁵ is hydrogen or alkyl,

R⁵¹, R⁵², R⁵³, and R⁵⁴ are each independently H, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, 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, hydroxy, epoxy, silane, siloxane, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, and urethane, or where each pair of adjacent substituents R⁵¹ and R⁵² and adjacent substituents R⁵³ and R⁵⁴ may independently form, together with the carbon atoms to which they are attached, a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more hetero atoms, more typically selected from divalent nitrogen, sulfur and oxygen atoms, as ring members. [00068] In one embodiment, the electrically conductive polymer comprises an electrically conductive copolymer that comprises at least one first monomeric unit per molecule that is according to formula (I), (I. a), (II), (III), or (III. a) or that is derived from a heteroaromatic monomer according to structure (IV) or (V) and further comprises one or more second monomeric units per molecule that differ in structure and/or composition from the first monomeric units. Any type of second monomeric units can be used, so long as it does not detrimentally affect the desired properties of the copolymer. In one embodiment, the copolymer comprises, based on the total number of monomer units of the copolymer, less than or equal to 50%, more typically less than or equal to 25%, even more typically less than or equal to 10 % of second monomeric units.

[00069] Exemplary types of second monomeric units include, but are not limited to those derived from alkenyl, alkynyl, arylene, and heteroarylene monomers, such as, for example, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylene vinylene, phenylene ethynylene, pyridine, diazines, and triazines, all of which may be further substituted, that are copolymerizable with the monomers from which the first monomeric units are derived.

[00070] In one embodiment, the electrically conductive copolymers are made by first forming an intermediate oligomer having the structure A-B-C, where A and C represent first monomeric units, which can be the same or different, and B

represents a second monomeric unit. The A-B-C intermediate oligomer can be prepared using standard synthetic organic techniques, such as Yamamoto, Stille, Grignard metathesis, Suzuki and Negishi couplings. The electrically conductive copolymer is then formed by oxidative polymerization of the intermediate oligomer alone, or by copolymerization of the intermediate oligomer with one or more additional monomers.

[00071 ] In one embodiment, the electrically conductive polymer comprises an electrically conductive copolymer of two or more monomers. In one embodiment, the monomers comprise at least one monomer selected from a thiophene monomer, a pyrrole monomer, an aniline monomer, and a polycyclic aromatic monomer.

[00072] In one embodiment, the weight average molecular weight of the electrically conductive polymer is from about 1000 to about 2,000,000 grams per mole, more typically from about 5,000 to about 1 ,000,000 grams per mole, and even more typically from about 10,000 to about 500,000 grams per mole.

[00073] The polymer film or polymer complex described herein may optionally further comprise one or more dopants. Suitable dopants include, but are not limited to, sulfonate anions, for example, para-toluene sulfonate anion; polymeric acid dopants, and the like.

[00074] In one embodiment, the polymer film or polymer complex comprises a polymeric acid dopant, typically a water soluble polymeric acid dopant. In one embodiment, the electrically conductive polymers used in the polymer films and polymer complexes are prepared by oxidatively polymerizing the corresponding monomers in aqueous solution containing a water soluble acid, typically a water- soluble polymeric acid. In one embodiment, the acid is a polymeric sulfonic acid. Some non-limiting examples of the acids are poly(styrenesulfonic acid) ("PSSA"), poly(2-acrylamido-2-methyl-1 -propanesulfonic acid) ("PAAMPSA"), and mixtures thereof. The acid anion provides the dopant for the conductive polymer. The oxidative polymerization is carried out using an oxidizing agent such as ammonium persulfate, sodium persulfate, and mixtures thereof. Thus, for example, when aniline is oxidatively polymerized in the presence of PMMPSA, the doped electrically conductive polymer blend PANI/PAAMPSA is formed. When

ethylenedioxythiophene (EDOT) is oxidatively polymerized in the presence of PSSA, the doped electrically conductive polymer blend PEDOT/PSS is formed. The conjugated backbone of PEDOT is partially oxidized and positively charged.

Oxidatively polymerized pyrroles and thienothiophenes also have a positive charge which is balanced by the acid anion. [00075] In one embodiment, the water soluble polymeric acid selected from the polysulfonic acids, more typically, poly(styrene sulfonic acid), or poly(acrylamido-2- methyl-1 -propane-sulfonic acid), or a polycarboxylic acid, such as polyacrylic acid polymethacrylic acid, or polymaleic acid.

[00076] The conductivity enhancing agent suitable for use in polymer films and polymer complexes in accordance with the present invention is generally not a polymer and is uncharged, i.e. does not comprise cations or anions. The

conductivity enhancing agent may act as a dopant, as defined herein. The conductivity enhancing agent comprises a compound selected from the group consisting of alkane, cycloalkane, cyclic ether, cyclic ester, arene, heteroarene, and mixtures thereof;

wherein when the conductivity enhancing agent comprises alkane, cycloalkane, cyclic ester, arene, and/or heteroarene, said alkane, cyclic ester, arene, and/or heteroarene are each substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl; and

wherein when the conductivity enhancing agent comprises a (Ci-C3)alkane, said (Ci-C3)alkane is substituted with at least two carboxy groups.

[00077] In one embodiment, the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl.

[00078] In one embodiment, the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

[00079] In one embodiment, the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6-naphthalenedicarboxylic acid; 1 ,4- naphthalenedicarboxylic acid; or a mixture thereof. [00080] In one embodiment, the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

[00081 ] In one embodiment, the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

[00082] In an embodiment, the conductivity enhancing agent comprises a compound represented by the structure

wherein R_z is alkyi, hydroxy, carboxy, aroyl, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl; and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyi, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

[00083] In an embodiment, R_z is alkyi, hydroxyl, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyi, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

[00084] In an embodiment, the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p-toluenesulfonic acid, 1 ,3,5-tris(4- carboxyphenyl)benzene, benzene-1 ,3,5-triacetic acid, or a mixture thereof.

[00085] In one embodiment, R_z is carboxy, and R_a, Rb, Rc, Rd, Re are each, independently, H, hydroxy, or carboxy. [00086] In an embodiment, the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, or a mixture thereof.

[00087] In one embodiment, R_z is carboxy, and R_a, Rb, R_c, Rd, Re are each, independently, H or hydroxy.

[00088] In an embodiment, the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, or a mixture thereof.

[00089] In an embodiment, the conductivity enhancing agent comprises salicylic acid.

[00090] In an embodiment, the conductivity enhancing agent comprises a heteroarene, typically furan, substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

[00091 ] In an embodiment, the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

[00092] In an embodiment, the conductivity enhancing agent comprises a cycloalkane, typically cyclohexane, substituted with at least one, more typically with at least two, even more typically with at least three, carboxy groups.

[00093] In an embodiment, the conductivity enhancing agent comprises 1 ,3,5- cyclohexanetricarboxylic acid.

[00094] In an embodiment, the conductivity enhancing agent comprises an alkane, typically a (C3-Ci2)alkane, substituted with at least one, more typically with at least two, even more typically with at least three, carboxy groups. [00095] In an embodiment, the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6-hexanetricarboxylic acid; or a mixture thereof.

[00096] In an embodiment, the conductivity enhancing agent comprises a cyclic ether, typically tetrahydrofu ran.

[00097] In an embodiment, the conductivity enhancing agent comprises a cyclic ester, typically a furanone, substituted with at least one hydroxyalkyl group. In an embodiment, the conductivity enhancing agent comprises ascorbic acid.

[00098] The polymer films and polymer complexes described herein may optionally further comprise one or more additional components, such as, for example one or more of ionic liquids, polymers, dyes, coating aids, conductive particles, conductive inks, conductive pastes, charge transport materials, crosslinking agents, inorganic materials, such as, for example, zinc oxides, cerium oxides, titanium oxides, and combinations thereof.

[00099] Ionic liquids are salts that have a melting point of less than or equal to 100°C. In one embodiment, the ionic liquid has a melting point of less than or equal to 75°C, more typically less than or equal to 50°C and even more typically less than or equal to 25°C.

[000100] In one embodiment, the ionic liquid comprises one or more organic or inorganic salts and have a melting point of less than or equal to 100°C.

[000101 ] In one embodiment, the ionic liquid consists entirely of cationic and anionic species.

[000102] Typical cations for suitable ionic liquid compounds include, for example: ammonium or tetraalkyl ammonium cations, such as, for example, tetramethyl ammonium, tetrabutyl ammonium, tetrahexyl ammonium, butyltrimethyl ammonium, and methyltrioctyl ammonium cations,

guanidinium cations such as, for example, N,N,N',N'-tetrahexyl-N",N"- dimethylguanidinium cations,

imidazolium cations, more typically, imidazolium cations that are substituted with from 1 to 3, more typically 2 to 3, alkyl, hydroxyalkyi, and/or aryl substituents per boron atom, such as, for example, 1 ,3-dimethyl-imidazolium, 1 -benzyl-3-methyl- imidazolium, 1 -butyl-3-methyl-imidazolium, 1 -ethyl-3-methyl-imidazolium, 1 -hexyl-3- methyl-imidazolium, 1 -methyl-3-propyl-imidazolium, 1 -methyl-3-octyl-imidazolium, 1 - methyl-3-tetradecyl-imidazolium, 1 -methyl-3-phenyl-imidazolium, 1 ,2,3-trimethyl- imidazolium, 1 ,2-methyl-3-octyl-imidazolium, 1 -butyl-2,3-dimethyl-imidazolium, 1 - hexyl-2,3-methyl-imidazolium, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium cations,

morpholinium cations, such as, for example, N-methyl-morpholinium and N- ethyl-morpholinium cations,

phosphonium cations, such as for example, tetrabutyl phosphonium and tributylmethyl phosphonium cations,

piperidinium cations, such as, for example, 1 -butyl-1 -methyl-piperidinium and 1 -methyl-1 -propyl-piperidinium cations,

pyradazinium cations,

pyrazinium cations, such as, for example, 1 -ethyl-4-methyl-pyrazinium, 1 - octyl-4-propyl-pyrazinium cations,

pyrazolium cations, such as, for example, 1 -ethyl-2,3,5-pyrazolinium cations, pyridinium cations, such as for example, N-butyl-pyridinium, and N-hexyl- pyridinium cations,

pyrimidinium cations, such as, for example, 1 -hexyl-3-propyl-pyrimidinium, 1 - ethyl-3-methyl-pyrimidinium cations,

pyrrolidinium cations, such as for example, 1 -butyl-1 -methyl-pyrrolidinium and 1 -methyl-1 -propyl-pyrrolidinium cations,

pyrrolium cations, such as for example, 1 ,1 -dimethyl-pyrrolium, 1 -methyl-1 - pentyl-pyrrolium cations, pyrrolinium cations,

sulfonium cations, such as, for example, trimethyl sulfonium cations, thiazolium cations,

oxazolium cations,

triazolium cations; and

inorganic cations, such as, for example, sodium (Na⁺), lithium (Li⁺), potassium (K⁺), rubidium (Rb⁺), cesium (Cs⁺), magnesium (Mg²⁺), calcium (Ca²⁺), strontium (Sr²⁺), barium (Ba²⁺), iron(lll) (Fe³⁺), cooper(ll) (Cu²⁺), silver(l) (Ag⁺), zinc(ll) (Zn²⁺), yttrium(lll) (Y³⁺), cobalt(ll) (Co²⁺), tungsten(lll) (W³⁺), zirconium(IV) (Zr⁴⁺), titanium(IV) (Ti⁴⁺), lanthanum(lll) (La³⁺), cerium(lll) (Ce³⁺), europium(lll) (Eu³⁺), aluminum(lll) (Al³⁺), gallium(ll l) (Ga³⁺), tin(ll) (Sn²⁺), tin(IV) (Sn⁴⁺), bismuth(lll) (Bi³⁺) and

antimony(lll) (Sb³⁺).

[000103] Typical anions for suitable ionic liquid compounds include, for example: borate anions, such as, for example, tetrafluoroborate, tetracyanoborate, tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,

alkyltrifluoroborate, perfluoroalkyltrifluoroborate, and alkenyltnfluoroborate anions carbonate anions such as, for example, hydrogen carbonate and

methylcarbonate anions,

carboxylate anions, such as, for example, salicylate, thiosalicylate, L-lactate, acetate, trifluroacetate, and formate anions,

chlorate anions,

cyanate anions, such as, for example, thiocyanate, dicyanamide, and tricyanomethane anions,

halide anions, such as, for example, fluoride, chloride, bromide, and iodide anions,

imide anions, such as, for example, imide, bis(fluoromethylsulfonyl)imide anions, and bis(trifluoromethylsulfonyl)imide anions,

nitrate anions,

phosphate anions, such as, for example, dihydrogen phosphate,

hexafluorophosphate, di(trifluromethyl)tetrafluorophosphate,

tris(trifluoromethyl)trifluorophosphate, tris(perfluoroalkyl)trifluorophosphate, tetra(trifluorornethyl)difluorophosphate, penta(trifluoromethyl)fluorphosphate, and hexa(thfluoromethyl)phosphate anions,

sulfate and sulfonate anions, such as, for example, trifluoromethanesulfonate, hydrogen sulfate, tosylate, (CrCi₂)alkylsulfate, and (Ci-Ci₂)alkylsulfonate anions, perfluoroalkyl β-diketonate anions, such as, for example, 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedionate, 1 ,1 ,1 ,5,5,5-hexafluoro-2,4- pentanedionate, and 4,4,4-trifluoro-1 -(2-thienyl)-1 ,3-butanedionate anions,

fluorohydrogenate anions, such as, for example, poly(hydrogen fluoride) fluoride anions,

fluorometallate anions, such as, for example, oxopentafluorotungstan (VI) anions, and

polyoxometallate anions.

[000104] The ionic liquid may comprise a mixture of ionic liquid compounds and thus a mixture of two or more of such cations and/or two or more of such anions.

[000105] In one embodiment, the ionic liquid comprises one or more compounds have an imidazolium cation. In one embodiment, the imidazolium cation is selected from 1 ,3-dimethylimidazolium, 1 -benzyl-3-methyl-imidazolium, 1 -butyl-3-methyl- imidazolium, 1 -ethyl-3-methyl-imidazolium, 1 -hexyl-3-methyl-imidazolium, 1 -methyl- 3-propyl-imidazolium, 1 -methyl-3-octyl-imidazolium, 1 -methyl-3-tetradecyl- imidazolium, 1 -methyl-3-phenylimidazolium, 1 ,2,3-trimethyl-imidazolium, 1 ,2-methyl- 3-octyl-imidazolium, 1 -butyl-2,3-dimethyl-imidazolium, 1 -hexyl-2,3-methyl- imidazolium, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium cations.

[000106] In one embodiment, the ionic liquid comprises sulfonate anion, sulfate anion, carboxylate anion, bis(trifluoromethylsulfonyl)imide anion, nitrate anion, nitro anion, halogen anion, hexafluorophosphate (PF₆ ^") anion, or tetrafluoroborate anion.

[000107] In one embodiment, the ionic liquid comprises para-toluene sulfonate anion, (CF₃S0₃)^" anion, (CH₃CH₂CH₂CH₂S0₃)^" anion, (CHF₂CF₂CF₂ CF₂CH₂S0₃)^" anion, bis(trifluoromethylsulfonyl)imide anion, or tetrafluoroborate anion. [000108] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a tetrafluoroborate anion, such as, for example, 1 ,3-dimethyl-imidazolium tetrafluoroborate, 1 -benzyl-3- methyl-imidazolium tetrafluoroborate, 1 -butyl-3-methyl-imidazolium tetrafluoroborate, 1 -ethyl-3-methyl-imidazolium tetrafluoroborate, 1 -hexyl-3-methyl-imidazolium tetrafluoroborate, 1 -methyl-3-propyl-imidazolium tetrafluoroborate, 1 -methyl-3-octyl- imidazolium tetrafluoroborate, 1 -methyl-3-tetradecyl-imidazolium tetrafluoroborate, 1 - methyl-3-phenyl-imidazolium tetrafluoroborate, 1 ,2,3-trimethyl-imidazolium

tetrafluoroborate, 1 ,2-methyl-3-octyl-imidazolium tetrafluoroborate, 1 -butyl-2,3- dimethyl-imidazolium tetrafluoroborate, 1 -hexyl-2,3-methyl-imidazolium

tetrafluoroborate, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium tetrafluoroborate, and mixtures thereof.

[000109] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a

bis(trifluoromethylsulfonyl)imide anion, such as, for example, 1 ,3-dimethyl- imidazolium bis(trifluoromethylsulfonyl)imide, 1 -benzyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, 1 -butyl-3-methyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3-methyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -hexyl-3-methyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -methyl-3-propyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -methyl-3-octyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -methyl-3-tetradecyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -methyl-3-phenyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 ,2,3-trimethyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 ,2-methyl-3-octyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -butyl-2,3-dimethyl-imidazolium

bis(trifluoromethylsulfonyl)imide, 1 -hexyl-2,3-methyl-imidazolium

bis(trifluoromethylsulfonyl)imide, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium bis(trifluoromethylsulfonyl)imide, and mixtures thereof. [0001 10] In one embodiment, the ionic liquid can be an ionic compound that has a melting point of less than 25°C, a viscosity at 20°C of less than or equal to about 100 centiPoise, and an ionic conductivity.

[0001 1 1 ] In one embodiment, the ionic liquid is an ionic compound that has a melting point of less than or equal to 25°C, such as, for example, 1 -ethyl-3-methyl- imidazolium tetrachloroaluminate, 1 -butyl-3-methyl-imidazolium tetrachloroaluminate, 1 -ethyl-3-methyl-imidazolium acetate, 1 -butyl-3-methyl-imidazolium acetate, 1 -ethyl- 3-methyl-imidazolium ethylsulfate, 1 -butyl-3-methyl-imidazolium methylsulfate, 1 - ethyl-3-methyl-imidazolium thiocyanate, 1 -butyl-3-methyl-imidazolium thiocyanate, 1 - ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, 1 -ethyl-3-methyl- imidazolium tetracyanoborate, 1 -butyl-1 -methyl-pyrrolidinium dicyanamide, 1 -ethyl-3- methyl-imidazolium tetrafluoroborate, 1 -ethyl-3-methyl-imidazolium trifluroacetate, 1 - ethyl-3-methyl-imidazolium bis(fluoromethylsulfonyl)imide, and mixtures thereof.

[0001 12] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a cyanate anion, such as, for example, 1 ,3-dimethyl-imidazolium dicyanate, 1 -benzyl-3-methyl-imidazolium thiocyanate, 1 -butyl-3-methyl-imidazolium tricyanomethane, 1 -ethyl-3-methyl- imidazolium dicyanate, 1 -hexyl-3-methyl-imidazolium thiocyanate, 1 -methyl-3-propyl- imidazolium tricyanomethane, 1 -methyl-3-octyl-imidazolium dicyanate, 1 -methyl-3- tetradecyl-imidazolium thiocyanate, 1 -methyl-3-phenyl-imidazolium dicyanate, 1 ,2,3- trimethyl-imidazolium thiocyanate, 1 ,2-methyl-3-octyl-imidazolium tricyanomethane, 1 -butyl-2,3-dimethyl-imidazolium dicyanate, 1 -hexyl-2,3-methyl-imidazolium thiocyanate, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium tricyanomethane, and mixtures thereof.

[0001 13] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a tetracyanoborate anion, such as, for example, 1 ,3-dimethyl-imidazolium tetracyanoborate, 1 -benzyl-3- methyl-imidazolium tetracyanoborate, 1 -butyl-3-methyl-imidazolium

tetracyanoborate, 1 -ethyl-3-methyl-imidazolium tetracyanoborate, 1 -hexyl-3-methyl- imidazolium tetracyanoborate, 1 -methyl-3-propyl-imidazolium tetracyanoborate, 1 - methyl-3-octyl-imidazolium tetracyanoborate, 1 -methyl-3-tetradecyl-imidazolium tetracyanoborate, 1 -methyl-3-phenyl-imidazolium tetracyanoborate, 1 ,2,3-trimethyl- imidazolium tetracyanoborate, 1 ,2-methyl-3-octyl-imidazolium tetracyanoborate, 1 - butyl-2,3-dimethyl-imidazolium tetracyanoborate, 1 -hexyl-2,3-methyl-imidazolium tetracyanoborate, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium tetracyanoborate, and mixtures thereof.

[0001 14] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a tetrakis-(p- (dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate anion, such as, for example, 1 ,3-dimethyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H- perfluorooctyl)silyl)phenyl)borate, 1 -benzyl-3-methyl-imidazolium tetrakis-(p- (dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -butyl-3-methyl- imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -ethyl-3-methyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H- perfluorooctyl)silyl)phenyl)borate, 1 -hexyl-3-methyl-imidazolium tetrakis-(p- (dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -methyl-3-propyl- imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -methyl-3-octyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H- perfluorooctyl)silyl)phenyl)borate, 1 -methyl-3-tetradecyl-imidazolium tetrakis-(p- (dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -methyl-3-phenyl- imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 ,2,3-trimethyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H- perfluorooctyl)silyl)phenyl)borate, 1 ,2-methyl-3-octyl-imidazolium tetrakis-(p- (dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -butyl-2,3-dimethyl- imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, 1 -hexyl-2,3-methyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H- perfluorooctyl)silyl)phenyl)borate, and 1 -(2-hydroxyethyl)-2,3-dimethyl-imidazolium tetrakis-(p-(dimethyl(1 H, 1 H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate, and mixtures thereof. [0001 15] In one embodiment, the ionic liquid comprises a salt of an alkyl-, hydroxyalkyl- and/or aryl-substituted imidazolium cation and a hexafluorophosphate anion, such as, for example, 1 ,3-dimethyl-imidazolium hexfluorophosphate, 1 -benzyl- 3-methyl-imidazolium hexfluorophosphate, 1 -butyl-3-methyl-imidazolium

hexfluorophosphate, 1 -ethyl-3-methyl-imidazolium hexfluorophosphate, 1 -hexyl-3- methyl-imidazolium hexfluorophosphate, 1 -methyl-3-propyl-imidazolium

hexfluorophosphate, 1 -methyl-3-octyl-imidazolium hexfluorophosphate, 1 -methyl-3- tetradecyl-imidazolium hexfluorophosphate, 1 -methyl-3-phenyl-imidazolium hexfluorophosphate, 1 ,2,3-trimethyl-imidazolium hexfluorophosphate, 1 ,2-methyl-3- octyl-imidazolium hexfluorophosphate, 1 -butyl-2,3-dimethyl-imidazolium

hexfluorophosphate, 1 -hexyl-2,3-methyl-imidazolium hexfluorophosphate, and 1 -(2- hydroxyethyl)-2,3-dimethyl-imidazolium hexfluorophosphate, and mixtures thereof.

[0001 16] The polymer films and polymer complexes described herein may each optionally further comprise one or more electrically conductive additives, such as, for example, metal particles, metal oxide particles, graphite particles, including graphite fibers, or carbon particles, including carbon fullerenes, and electrically conductive nanostructures. Suitable fullerenes include for example, C60, C70, and C84 fullerenes, each of which may be derivatized, for example with a (3- methoxycarbonyl)-propyl-phenyl ("PCBM") group, such as C60-PCBM, C-70-PCBM and C-84 PCBM derivatized fullerenes.

[0001 17] As used herein, the term "nanostructures" generally refers to nano- sized structures, at least one dimension of which is less than or equal to 500 nm, more typically, less than or equal to 250 nm, or less than or equal to 100 nm, or less than or equal to 50 nm, or less than or equal to 25 nm.

[0001 18] The electrically conductive nanostructures can be of any shape or geometry, more typically of anisotropic geometry. Typical anisotropic nanostructures include nanofibers, nanowires and nanotubes. [0001 19] The electrically conductive nanostructures can be formed of any electrically conductive material, such as for example, metallic materials, such as silver, or non-metallic materials, such as carbon or graphite. Metallic electrically conductive nanostructures include, for example, silver nanowires or silver nanotubes. Non-metallic electrically conductive nanostructures include carbon nanostructures, for example, carbon nanotubes. Suitable carbon nanotubes include single wall carbon nanotubes having an armchair, zigzag or chiral structure, as well as multiwall carbon nanotubes, including double wall carbon nanotubes, and mixtures thereof.

[000120] The one or more electrically conductive additives may comprise a mixture of such additives, such as a mixture of carbon fibers and silver nanowires.

[000121 ] In one embodiment, the polymer film and polymer complex may each optionally comprise up to about 65 wt%, more typically from about 12 wt% to about 62 wt% carbon particles, more typically carbon nanotubes, and even more typically multi-wall carbon nanotubes, based on 100 wt% of the polymer film or complex.

[000122] The polymer film described herein may have any arbitrary thinkness adapted according to its use. In one embodiment, the polymer film has a thickness of from about 1 nm to 1000 nm, typically from about 5 nm to 300 nm, more typically from about 10 nm to about 100 nm, even more typically from about 20 nm to about 40 nm.

[000123] The sheet resistance may be measured using methods known to those of ordinary skill in the art. For example, a four probe tester, such as a Jandel RM3- AR instrument, may be used according to known methods. The polymer films decribed herein exhibit a sheet resistance of less than or equal to 30000 ohms per square ("Ω/D"), or less than or equal to 200 Ω/D, or less than or equal to 150 Ω/D, or less than or equal to 100 Ω/D, or less than or equal to 50 Ω/D. In an embodiment, the sheet resistance of the polymer film described herein is from about 1 to about 30000 Ω/D, typically from about 1 to about 200 Ω/D, more typically from about 1 to about 150 Ω/D, even more typically from about 1 to about 50 Ω/D .

[000124] The transmittance and haze of the polymer films described herein may be determined according to methods known in the art. For example, a Haze-guard Plus hazemeter (BYK) may be used. The polymer films described herein exhibit a total transmittance (with or without substrate) of greater than or equal to 1 %, or greater than or equal to 50%, or greater than or equal to 70%, or greater than or equal to 80%, or greater than or equal to 90%, greater than or equal to 95%.

[000125] In an embodiment, the sheet resistance of the polymer film described herein is from about 1 to about 30000 Ω/D, or from about 1 to about 200 Ω/D, or from about 1 to about 150 Ω/D, or from about 1 to about 50 Ω/D and a total transmittance (with or without substrate) of greater than or equal to 1 %, or greater than or equal to 50%, or greater than or equal to 70%, or greater than or equal to 80%, or greater than or equal to 90%, or greater than or equal to 95%.

[000126] In one embodiment, the respective polymer film of the present invention and polymer film component of the electronic device of the present invention each exhibit a sheet resistance of less than or equal to 150 Ω and a total transmittance of greater than or equal to 80%.

[000127] The present invention relates to a process for producing a polymer film or polymer complex as described herein, the process comprising:

(1 ) treating a pristine polymer film or pristine polymer complex with at least one conductivity enhancing agent, or a solution thereof,

(2) optionally washing the polymer film or polymer complex obtained in step (1 ),

thereby producing the polymer film or polymer complex.

[000128] The pristine polymer film may be obtained by methods known to those of ordinary skill in the art. For example, a polymer composition free of conductivity enhancing agent comprising an electrically conductive polymer, as described herein, and a liquid medium may be deposited on a substrate using conventional deposition techniques, such as spin coating, screen printing, rod or bar coating, roll-to-roll coating, doctor-blade coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating. The substrate can be flexible or rigid, organic or inorganic. Suitable substrate materials include, for example, glass, ceramic, metal, and plastic films. The liquid medium is then removed, typically by heating, to form the pristine polymer film.

[000129] In one embodiment, the liquid medium is an aqueous medium that comprises water. In one embodiment, the liquid medium is an aqueous medium that consists essentially of water. In one embodiment, the liquid medium is an aqueous medium that consists of water. In one embodiment, the liquid medium is a nonaqueous medium that comprises one or more water miscible organic liquids. In one embodiment, the liquid medium is an aqueous medium that comprises water and, optionally, one or more water miscible organic liquids. Suitable water miscible organic liquids include polar aprotic organic solvents, such as, for example, dimethyl sulfoxide and dimethyl 2-methylglutarate (marketed as Rhodiasolv® IRIS), polar protic organic solvents, such as, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and mixtures thereof. In one embodiment, the liquid medium comprises, based on 100 wt% of the liquid medium, from about 10 to 100 wt%, more typically from about 50 to 100 wt%, and even more typically, from about 90 to 100 wt%, water and from 0 to about 90 wt%, more typically from 0 pbw to about 50 wt%, and even more typically from 0 to about 10 wt% of one or more water miscible organic liquids.

[000130] In one embodiment, the liquid medium may optionally further comprise, based on 100 wt% of the liquid medium, from greater than 0 to about 15 wt%, more typically from about 1 to about 10 wt%, of an organic liquid selected from high boiling polar organic liquids, typically having a boiling point of at least 120°C, more typically from diethylene glycol, meso-erythritol, 1 ,2,3,4, -tetrahydroxybutane, 2-nitroethanol, glycerol, sorbitol, dimethyl sulfoxide, tetrahydrofuran, dimethyl formamide, and mixtures thereof.

[000131 ] The pristine polymer complex may be obtained by methods known to those of ordinary skill in the art. For example, to obtain a pristine polymer gel, a polymer composition free of conductivity enhancing agent comprising an electrically conductive polymer, as described herein, and a liquid medium, is contacted with an amount of ionic liquid, as described herein, effective to gel the electrically conductive polymer. To obtain a pristine polymer foam, the liquid remaining on or in the pristine polymer gel is removed by, typically, but not limited to, lyophilization or heating.

[000132] The formation of the pristine polymer complexes can be characterized as a two-step reaction. In the first step, some time after combining the ionic liquid and the electrically conductive polymer, the resulting composition becomes viscous. In the second step, the polymer composition visibly contracts in the liquid medium, giving rise to a gel surrounded by a liquid phase.

[000133] In one embodiment, the polymer complex described herein is a polymer gel.

[000134] In one embodiment, the polymer complex described herein is a polymer foam.

[000135] In one embodiment, the polymer complexes described herein comprise an interaction between the electrically conductive polymer and the ionic liquid effective to gel the electrically conductive polymer. In one embodiment, the polymer complexes have porous structure, a high strength to weight and surface area to volume ratios, and high electrical conductivity. In one embodiment, the storage modulus, G', of the polymer complex exceeds the loss modulus, G", of the polymer complex at any angular frequency within a range of from about 0.01 to about 100 radians/second, as determined by dynamic oscillatory measurements using a dynamic mechanical analysis instrument, such as, for example, an AR-G2. [000136] An amount of ionic liquid effective to gel the electrically conductive polymer refers to the minimum amount of ionic liquid required to be combined with the electrically conductive polymer to bring about gelation of the electrically conductive polymer. The effective amount of ionic liquid required to gel the electrically conductive polymer may be provided neat or in a solution. The effective amount of ionic liquid required to gel the electrically conductive polymer will depend on the identity of the polymer and the ionic liquid, and may be determined by one of ordinary skill in the art as desired for a particular application, for example, by combining varying amounts of ionic liquid, or a solution thereof, with electrically conductive polymer and observing the resulting polymer composition.

[000137] Once the electrically conductive polymer and ionic liquid are contacted in the liquid medium, for example, by adding the ionic liquid, or a solution thereof, to a liquid medium containing the electrically conductive polymer, the resulting polymer composition may optionally be mechanically stirred. The gelation occurs with or without stirring so long as an amount of ionic liquid effective to gel the electrically conductive polymer is used.

[000138] The polymer gel that is formed by contacting the ionic liquid with the electrically conductive polymer may optionally be rinsed. In an embodiment, the polymer gel is rinsed with a rinse liquid, as described herein, by any known method, such as, for example, by immersing the polymer complex in an excess of rinse liquid. The rinsing of the polymer gel that is formed by contacting the ionic liquid with the electrically conductive polymer may also be performed with or without agitation. Agitation may be accomplished using any method known to those of ordinary skill in the art, such as, for example, stirring using a magnetic stirrer, stirring at high speed using a vortex, or the like.

[000139] Any liquid, such as, for example, liquid medium, rinse liquid, or a mixture thereof, remaining on or in the polymer gel may be removed from the polymer gel. In an embodiment, a polymer foam is formed. Any method known to those of ordinary skill in the art effective to remove any liquid from the polymer gel may be used, such as, for example, freeze-drying (lyophilization), heating under an infrared lamp, or the like.

[000140] The treatment of the pristine polymer film or pristine polymer complex with conductivity enhancing agent may be achieved by any suitable method known to those of ordinary skill in the art. For example, the conductivity enhancing agent, or a solution thereof, may be delivered dropwise to at least one of the surfaces of the pristine polymer film or pristine polymer complex as desired. Alternatively, the pristine polymer film or pristine polymer complex may also be dipped or immersed in the conductivity enhancing agent, or a solution thereof.

[000141 ] In an embodiment, the pristine polymer film or pristine polymer complex is treated with a solution comprising the conductivity enhancing agent and a solvent.

[000142] The solvent component of the conductivity enhancing agent solution may be any solvent, or mixture of solvents, in which the conductivity enhancing agent is soluble. Suitable solvents include, but are not limited to, water; polar aprotic organic solvents, such as, for example, dimethyl sulfoxide, dichloromethane, ethyl acetate, acetone, tetrahydrofuran, and dimethyl 2-methylglutarate (marketed as Rhodiasolv® IRIS); polar protic organic solvents, such as, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; non-polar organic solvents, such as hexanes, cyclohexane, benzene, toluene, chloroform, and diethyl ether; and mixtures thereof.

[000143] The concentration of the conductivity enhancing agent in solution, based on 100 wt% of the solution, is from greater than 0 wt% to about 50 wt%, typically about 0.01 wt% to about 30 wt%, more typically from about 0.1 wt% to about 20 wt%.

[000144] The conductivity enhancing agent is as described herein. [000145] The polymer film or polymer complex obtained in the treatment step may optionally be washed with a rinse liquid, and may be accomplished using any suitable methods known to those of ordinary skill in the art. For example, the film or complex may be dipped or immersed in an excess of rinse liquid. The rinse liquid may be any solvent, or mixture of solvents, in which the polymer film or polymer complex is not soluble. Suitable solvents for use in the rinse liquid include, but are not limited to, water; polar aprotic organic solvents, such as, for example, dimethyl sulfoxide, dichloromethane, ethyl acetate, acetone, tetrahydrofuran, and dimethyl 2- methylglutarate (marketed as Rhodiasolv® IRIS); polar protic organic solvents, such as, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; non-polar organic solvents, such as hexanes, cyclohexane, benzene, toluene, chloroform, and diethyl ether; and mixtures thereof.

[000146] Following the treatment step or the optional washing step, or following both the treatment step and the optional washing step, the polymer film or polymer complex may be dried. Any method known to those of ordinary skill in the art effective to remove liquid from the polymer film or polymer complex may be used, such as, for example, heating.

[000147] The polymer film according to the present invention typically exhibits high conductivity (low sheet resistance) and high optical transparency and is useful as a layer in an electronic device in which the high conductivity is desired in combination with optical transparency.

[000148] In one embodiment, the polymer films described herein may be prepared from a polymer composition.

[000149] Thus, the present invention relates to a polymer composition

comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants, (c) at least one conductivity enhancing agent, and

(d) a liquid medium.

[000150] The at least one electrically conductive polymer, at least one conductivity enhancing agent, and liquid medium are each as described herein. Optionally, the polymer composition may comprise one or more polymeric acid dopants, as described herein.

[000151 ] In an embodiment, the polymer composition described herein comprises, based on 100 wt% of the polymer composition:

(a) from about 0.1 to about 10.0 wt%, more typically from about 0.1 to about 5.0 wt%, and even more typically from about 0.1 to about 3.0 wt% of electrically conductive polymer,

(b) from about 0 to about 10.0 wt%, more typically from about 0.1 to about 5.0 wt%, and even more typically from about 0.1 to about 3.0 wt% of polymeric acid dopant,

(c) from about 0.01 to about 70.0 wt%, more typically from about 0.1 to about 10.0 wt%, and even more typically from about 0.2 to about 5.0 wt% of conductivity enhancing agent,

(d) from about 1 .0 to about 99.0 wt%, more typically from about 50.0 to about 99.0 wt%, and even more typically from about 80.0 to about 99.0 wt% of liquid medium.

[000152] In an embodiment, the polymer composition described herein, comprises, based on 100 wt% of the polymer composition:

(a) from about 0.1 to about 10.0 wt% of electrically conductive polymer,

(b) from about 0 to about 10.0 wt% of polymeric acid dopant,

(c) from about 0.01 to about 70.0 wt% of conductivity enhancing agent,

(d) from about 1 .0 to about 99.0 wt% of liquid medium.

[000153] The present invention also relates to a process for producing a polymer film as described herein, the process comprising: (1 b) forming a layer of a polymer composition described herein, (2b) removing the liquid medium from the layer,

thereby producing the polymer film.

[000154] The present invention relates to electronic devices comprising the polymer films or polymer complexes described herein.

[000155] The electronic device in accordance with the present invention may be any device that comprises one or more layers of semiconductor materials and makes use of the controlled motion of electrons or ions through such one or more layers, such as, for example:

a device that converts mechanical perturbation into a change in electrical conductivity, such as, for example, a piezoresistive device,

a device that converts electrical energy into radiation, such as, for example, a light-emitting diode, light emitting diode display, diode laser, a liquid crystal display, or lighting panel,

a device that detects signals through electronic processes, such as, for example, a photodetector, photoconductive cell, photoresistor, photoswitch, phototransistor, phototube, infrared ("IR") detector, biosensor, or a touch screen display device,

a device that converts radiation into electrical energy, such as, for example, a photovoltaic device or solar cell,

a device that converts a temperature gradient (eg., heat flow) into electrical energy or converts electrical energy into a temperature gradient, such as a thermoelectric device, including, but not limited to, a thermoelectric cooler, a thermoelectric heater, or thermoelectric generator,

a device that stores and/or provides electrical energy, such as, for example, a battery,

a device that includes one or more electronic components with one or more semiconductor layers, such as, for example, a transistor or diode, and a device that exhibits a reversible change in optical properties, such as color, optical transmission, absorption, reflectance, and/or emittance, such as, for example, an electrochromic device.

[000156] In one embodiment, the electronic device described herein is an electronic device 140, as shown in FIG. 1 , having an anode layer 141 , an

electroactive layer 144, and a cathode layer 146 and optionally further having a buffer layer or hole injection layer 142, hole transport layer 143, and/or electron injection/transport layer or confinement layer 145, wherein at least one of the layers of the device is a polymer film or polymer complex described herein. The device 140 may further include a support or substrate (not shown), that can be adjacent to the anode layer 141 or the cathode layer 146, more typically, adjacent to the anode layer 141 . The support can be flexible or rigid, organic or inorganic. Suitable support materials include, for example, glass, ceramic, metal, and plastic films.

[000157] In some embodiments, optional hole transport layer 143 is present, either between anode layer 141 and electroactive layer 144, or, in those

embodiments that comprise buffer layer 142, between buffer layer 142 and electroactive layer 144. Hole transport layer 143 may comprise one or more hole transporting molecules and/or polymers. Commonly used hole transporting molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)- triphenylamine, 4,4',4"-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine, Ν,Ν'- diphenyl-N,N'-bis(3-methylphenyl)-(1 ,1 '-biphenyl)-4,4'-diamine, 1 ,1 -bis((di-4- tolylamino)phenyl)cyclohexane, N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)- (1 ,1 '-(3,3'-dimethyl)biphenyl)-4,4'-diamine, tetrakis-(3-methylphenyl)-N,N,N',N'-2,5- phenylenediamine, .alpha-phenyl-4-N,N-diphenylaminostyrene, p- (diethylamino)benzaldehyde diphenylhydrazone, triphenylamine, bis(4-(N,N- diethylamino)-2-methylphenyl)(4-methylphenyl)methane, 1 -phenyl-3-(p- (diethylamino)styryl)-5-(p-(diethylamino)phenyl)pyrazoline, 1 ,2-trans-bis(9H- carbazol-9-yl)cyclobutane, N,N,N',N'-tetrakis(4-methylphenyl)-(1 ,1 '-biphenyl)-4,4'- diamine, N,N'-bis(naphthalen-1 -yl)-N,N'-bis-(phenyl)benzidine, and porphyrinic compounds, such as copper phthalocyanine. Commonly used 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.

[000158] In some embodiments, optional hole injection layer 142 is present, and is disposed between anode layer 141 and electroactive layer 144, or, in those embodiments that comprise hole transport layer 143, between anode layer 141 and hole transport layer 143. The optional hole injection layer 142 may comprise the polymer film or polymer complex described herein.

[000159] The composition of electroactive layer 144 depends on the intended function of device 140, for example, electroactive layer 144 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), or 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). In one embodiment, electroactive layer 144 comprises an organic electroluminescent ("EL") material, such as, for example, electroluminescent small molecule organic compounds, electroluminescent metal complexes, and

electroluminescent conjugated polymers, as well as mixtures thereof. Suitable EL small molecule organic compounds include, for example, pyrene, perylene, rubrene, and coumarin, as well as derivatives thereof and mixtures thereof. Suitable EL metal complexes include, for example, metal chelated oxinoid compounds, such as tris(8- hydroxyquinolate)aluminum, cyclo-metallated iridium and platinum

electroluminescent compounds, such as complexes of iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., U.S. Pat. No. 6,670,645, and organometallic complexes such as those described in, for example, Published PCT Applications WO 03/008424, as well as mixtures any of such EL metal complexes. Examples of EL conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, and poly(p-phenylenes), as well as copolymers thereof and mixtures thereof.

[000160] Optional layer 145 can function as an electron injection/transport layer and/or a confinement layer. More specifically, layer 145 may promote electron mobility and reduce the likelihood of a quenching reaction if layers 104 and 106 would otherwise be in direct contact. Examples of materials suitable for optional layer 105 include, for example, metal chelated oxinoid compounds, such as bis(2- methyl-8-quinolinolato)(para-phenyl-phenolato)aluminum(lll) and tris(8- hydroxyquinolato)aluminum, tetrakis(8-hydroxyquinolinato)zirconium, azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole, 3-(4- biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole, and 1 ,3,5-tri(phenyl-2- benzimidazole)benzene, quinoxaline derivatives such as 2,3-bis(4- fluorophenyl)quinoxaline, phenanthroline derivatives such as 9,10- diphenylphenanthroline and 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline, and as well as mixtures thereof. Alternatively, optional layer 145 may comprise an inorganic material, such as, for example, BaO, LiF, Li₂0.

[000161 ] Cathode layer 146 can be any metal or nonmetal having a lower work function than anode layer 141 . In one embodiment, anode layer 141 has a work function of greater than or equal to about 4.4 eV and cathode layer 146 has a work function less than about 4.4 eV. Materials suitable for use as cathode layer 146 are known in the art and include, for example, alkali metals of Group 1 , such as Li, Na, K, Rb, and Cs, Group 2 metals, such as, Mg, Ca, Ba, Group 12 metals, lanthanides such as Ce, Sm, and Eu, and actinides, as well as aluminum, indium, yttrium, and combinations of any such materials. Specific non-limiting examples of materials suitable for cathode layer 146 include, but are not limited to, Barium, Lithium, Cerium, Cesium, Europium, Rubidium, Yttrium, Magnesium, Samarium, and alloys and combinations thereof. Cathode layer 146 is typically 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 141 . [000162] In one embodiment, an encapsulation layer (not shown) is deposited over cathode layer 146 to prevent entry of undesirable components, such as water and oxygen, into device 140. Such components can have a deleterious effect on electroactive layer 144. In one embodiment, the encapsulation layer is a barrier layer or film. In one embodiment, the encapsulation layer is a glass lid.

[000163] Though not shown in FIG. 1 , it is understood that device 140 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 141 , buffer layer or hole injection layer 142, hole transport layer 143, electron transport layer 145, cathode layer 146, and any additional 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 in the art.

[000164] The various layers of the electronic device can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. 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. 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. [000165] In one embodiment of the device 140, the different layers have the following range of thicknesses:

anode layer 101 , typically 500-5000 Angstroms ("A"), more typically, 1000- 2000 A,

optional buffer layer 102: typically 50-2000 A, more typically, 200-1000 A, optional hole transport layer 103: typically 50-2000 A, more typically, 100- 1000 A,

photoactive layer 104: typically, 10-2000 A, more typically, 100-1000 A, optional electron transport layer: typically 105, 50-2000 A, more typically, 100- 1000 A, and

cathode layer 106: typically 200-10000 A, more typically, 300-5000 A.

As is known in the art, 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 appropriate ratio of layer thicknesses will depend on the exact nature of the device and the materials used.

[000166] In one embodiment, the electronic device of the present invention, comprises:

(a) an anode or combined anode and buffer layer 141 ,

(b) a cathode layer 146,

(c) an electroactive layer 144, disposed between anode layer 141 and cathode layer 146,

(d) optionally, a buffer layer or hole transport layer 142, typically disposed

between anode layer 141 and electroactive layer 144,

(e) optionally, a hole transport layer 143, typically disposed between anode layer 141 and electroactive layer 144, or if buffer layer 142 is present, between buffer layer 142 and electroactive layer 144, and

(f) optionally an electron injection layer 145, typically disposed between

electroactive layer 144 and cathode layer 146,

wherein at least one of the layers of the device comprises a polymer film or polymer complex described herein. [000167] In one embodiment, the electronic device of the present invention is a device for converting radiation into electrical energy, and comprises an anode 141 that comprises a polymer film or polymer complex according to the present invention, a cathode layer 146 , an electroactive layer 144 comprising a material that is capable of converting radiation into electrical energy, disposed between the anode layer 141 layer and the cathode layer 146, and optionally further comprising a buffer layer 142, a hole transport layer 143, and/or an electron injection layer 145.

[000168] In operation of one embodiment of device 140, such as a device for converting electrical energy into radiation, a voltage from an appropriate power supply (not depicted) is applied to device 140 so that an electrical current passes across the layers of the device 140 and electrons enter electroactive layer 144, and are converted into radiation, such as in the case of an electroluminescent device, a release of photon from electroactive layer 144.

[000169] In operation of another embodiment of device 140, such as device for converting radiation into electrical energy, device 140 is exposed to radiation impinges on electroactive layer 144, and is converted into a flow of electrical current across the layers of the device.

[000170] In one embodiment, the electronic device 140 is a thermoelectric device comprising an anode 141 , a cathode layer 146 and an electroactive layer 144 disposed between the anode layer and cathode layer, wherein at least one of the anode layer, the cathode layer, and electroactive layer comprises a polymer film or polymer complex described herein. In an embodiment, the electroactive layer 144 is an electrolyte layer. The thermoelectric device according to the present invention may further comprise optional layers, the use of which may be determined by those having ordinary skill in the art. Generally, a thermoelectric device is a semiconductor device that converts a temperature difference into electricity, or vice versa.

[000171 ] The anode layer 141 and cathode layer 146, which are electrodes in this embodiment, are in contact with the electroactive layer 144, typically an electrolyte layer, such that an applied temperature gradient over the electroactive layer 144 or an applied voltage over the electrodes facilitate transport of ions to and/or from the electrodes via the the electroactive layer 144, typically an electrolyte layer, thereby facilitating a reduction-oxidation (redox) reaction at the electrodes.

[000172] In an embodiment, the anode layer 141 and cathode layer 146 of the thermoelectric device may comprise a polymer film or polymer complex described herein. The electrodes may further comprise materials known to those skilled in the art to be useful in the electrodes of a thermoelectric device. Such materials can be used alone or in combination, as in mixtures or composites. Suitable electrode materials include, but are not limited to carbon materials with high specific surface area, for example activated carbon, carbon aerogels, carbon nanotubes, templated porous carbons, carbon nanofibers and graphene networks; and metal oxides such as, for example, Ru0₂, Ir0₂, Mn0₂, NiO, Co₂0₃, Sn0₂, V₂0₅, and MoO.

[000173] The electroactive layer 144, typically an electrolyte layer, can be any material capable of conducting ions from one electrode to the other opposite electrode in the thermoelectric device. In one embodiment, the electroactive layer 144 comprises a polymer film or polymer complex described herein.

[000174] Thermoelectricity allows for reversible interplay between heat flow (temperature gradient) and charge flow (electricity current). A thermoelectric effect may be obtained in various ways. A thermoelectric effect wherein a heat flow transport charge carriers, thus producing a voltage, is known as the Seebeck effect. A device that takes advantage of the Seebeck effect is used as an electric power source, which is generally known as a thermoelectric generator. Conversely, the reverse effect exists wherein an electrical current is used to generate heat flow (Peltier effect), thus, creating a temperature gradient. Thermoelectric coolers take advantage of the Peltier effect for pumping heat with electrical energy. A third kind of thermoelectric effect is the so called Thomson effect wherein a temperature gradient together with an electrical current cause heat to be generated and absorbed, respectively. [000175] In an embodiment, the thermoelectric device described herein is a thermoelectric generator. In one embodiment, the thermoelectric device described herein is a thermoelectric cooler.

[000176] In one embodiment, the electronic device 140 is a battery cell comprising an anode layer 141 , a cathode layer 146 and an electroactive layer 144 disposed between the anode layer and cathode layer, wherein at least one of the anode layer, the cathode layer, and electrolyte layer comprises a polymer film or polymer complex described herein. In an embodiment, the electroactive layer 144 is an electrolyte layer. The battery cell according to the present invention may further comprise optional layers, the use of which may be determined by those having ordinary skill in the art.

[000177] The battery cell comprising an anode 141 , a cathode layer 146 and an electroactive layer 144, typically an electrolyte layer, disposed between the anode layer and cathode layer, wherein at least one of the anode layer, the cathode layer, and electrolyte layer comprises a polymer film or polymer complex described herein may be made to have any arbitrary shape that is rigid, flexible, bendable, and/or twistable using methods known to a person of ordinary skill in the art. For example, the anode 141 , the cathode 146, and the electroactive layer 144 may be formed into a cable-type shape wherein the anode 141 , cathode 146, the electroactive layer 144, and any optional layers, are formed into concentric cylindrical layers in a cable-type shape that is flexible, bendable, and/or twistable. The shape of the battery cell may be adapted for any application, and the battery cell may be made to be wearable and/or waterproof.

[000178] The battery cell described herein may be part of a battery pack comprising one or more battery cells. The battery pack may be made to have any arbitrary shape that is rigid, flexible, bendable, and/or twistable using methods known to a person of ordinary skill in the art. [000179] The anode layer 141 and the cathode layer 146 of the battery cell may optionally contain a base metal or a material into/from which ions of a base metal can be inserted and desorbed.

[000180] In one embodiment, the cathode layer 146 comprises a polymer film or polymer complex described herein. In one embodiment, the cathode layer 146 may comprise transition-metals, metal oxides, for example, lithium nickel oxide or a lithium metal oxide, and the like. In another embodiment, the cathode layer 146 may comprise aluminum, titanium, nickel, and/or alloys of these metals.

[000181 ] In one embodiment, the anode layer 141 comprises a polymer film or polymer complex described herein. In one embodiment, the anode layer 141 may comprise graphite, copper, and the like.

[000182] The electroactive layer 144, typically an electrolyte layer, can be any material capable of conducting ions from one electrode to the other opposite electrode in a battery cell. In one embodiment, the electroactive layer 144 comprises a polymer film or polymer complex described herein.

[000183] In an embodiment, the electronic device 140 is a piezoresistive device comprising an anode layer 141 , a cathode layer 146, and an electroactive layer 144. In an embodiment, the electroactive layer 144 of the piezoresistive device comprises the polymer film or polymer complex according to the present invention.

[000184] Piezoresistive devices operate on the principle that one or more materials contained therein exhibit a change in electrical resistance when the one or more materials are mechanically strained, for example, by stretching or by compression. Piezoresistive devices include, but are not limited to, pressure sensors, tactile sensors, biosensors, and the like.

[000185] The anode layer 141 and the cathode layer 146 of the piezoresistive device may be positioned such that they are physically isolated from one another but maintain electrical contact with the electroactive layer 144. Each of the anode layer 141 and the cathode layer 146 may be chosen from the same or different materials, as long as they are sufficiently electrically conductive.

[000186] The piezoresistive device described herein may further comprise an ohmmeter to measure the resistance between the anode and cathode. For example, the electrical resistance of the electroactive layer in the piezoresistive device will change thereby eliciting a response from the coupled ohmmeter. This resistance measurement can be calibrated to the pressure applied and used to generate standardized data sets. These data sets could then be used to provide a direct readout of the pressure applied on the device.

[000187] The piezoresistive device of the present invention is useful in a wide range of applications in areas such as, for example, biosensing, smart textiles, tactile sensing, and pressure sensing.

[000188] In an embodiment, the electronic device 140 is an electrochromic device comprising an anode layer 141 , a cathode layer 146, a buffer layer 142, and an electroactive layer 144, disposed between the buffer layer and cathode layer, wherein at least one of the anode layer, the cathode layer, the buffer layer, and electroactive layer comprises a polymer film or polymer complex described herein. The electrochromic device according to the present invention may further comprise optional layers, the use of which may be determined by those having ordinary skill in the art. In an embodiment, the buffer layer 142 may act to facilitate the flow of ions and/or electrons to and from the electroactive layer.

[000189] An electrochromic device exhibits a reversible change in optical properties, such as color, optical transmission, absorption, reflectance, and/or emittance. The electrochromic device of the present invention is useful in a wide range of applications in areas such as, for example, windows that can be darkened or in variable reflectance mirrors in vehicles. [000190] The present invention is further illustrated by the following non-limiting examples.

[000191 ] Examples.

[000192] PEDOT:PSS pristine films were prepared from Clevios™ PH1000 aqueous dispersion (1 .3% PEDOT:PSS aqueous dispersion; available from

Heraeus) by bar coating using different wet coating thickness bars: 20 and 40 μΐη. The films were then dried between 1 10 and 130 °C for 30 minutes. After drying, the pristine films were dipped in a solution of salicylic acid (SA) in water then removed and left to dry at 130 °C for 10 minutes. Other films were also prepared and dipped in SA prepared in pure ethanol then washed after dipping with various solvents. Sheet resistance was measured using a Jandel RM3-AR four-probe tester, and transparency and haze were measured using a Haze-guard Plus hazemeter (BYK). The resistance, transparency and haze were measured before and after treatment. The results are as indicated in Table 1 .

Table 1 : Resistance, Transparency and Haze values of PEDOT:PSS films after dipping in different SA solutions.

SA (added 26000 86.8 0.48 directly into

PEDOT:PSS

dispersion)

Claims

WHAT IS CLAIMED IS:

1 . A polymer film comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants, and

(c) at least one conductivity enhancing agent;

wherein the conductivity enhancing agent comprises a compound selected from the group consisting of alkane, cycloalkane, cyclic ether, cyclic ester, arene, heteroarene, and mixtures thereof;

wherein when the conductivity enhancing agent comprises alkane, cycloalkane, cyclic ester, arene, and/or heteroarene, said alkane, cyclic ester, arene, and/or heteroarene are each substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl; and

2. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

3. The polymer film of claim 2, wherein the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

4. The polymer film of claim 3, wherein the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6-naphthalenedicarboxylic acid; 1 ,4- naphthalenedicarboxylic acid; or a mixture thereof.

5. The polymer film of claim 2, wherein the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

6. The polymer film of claim 5, wherein the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

7. The polymer film of claim 2, wherein the conductivity enhancing agent comprises a compound represented b the structure

wherein R_z is alkyl, hydroxy, carboxy, aroyl, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl; and R_a, R_b, R_c, R_d, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

8. The polymer film of claim 7, wherein R_z is alkyl, hydroxy, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, R_b, R_c, R_d, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

9. The polymer film of claim 8, wherein the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p-toluenesulfonic acid, 1 ,3,5-tris(4-carboxyphenyl)benzene, benzene-1 ,3, 5-th ace tic acid, or a mixture thereof.

10. The polymer film of claim 7, wherein R_z is carboxy, and R_a, R_b, R_c, R_d, Re are each, independently, H, hydroxy, or carboxy.

1 1 . The polymer film of claim 10, wherein the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, or a mixture thereof.

12. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises a heteroarene substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

13. The polymer film of claim 12, wherein the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

14. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises a cycloalkane substituted with at least one carboxy group.

15. The polymer film of claim 14, wherein the conductivity enhancing agent comprises 1 ,3,5-cyclohexanetricarboxylic acid.

16. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises an alkane substituted with at least one carboxy group.

17. The polymer film of claim 16, wherein the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6-hexanetricarboxylic acid; or a mixture thereof.

18. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises a cyclic ether.

19. The polymer film of claim 1 , wherein the conductivity enhancing agent comprises a cyclic ester substituted with at least one hydroxyalkyl group.

20. The polymer film according to any one of claims 1 -19, wherein the at least one electrically conductive polymer comprises at least one polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S.

21 . The polymer film according to claim 20, wherein the at least one

polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S, comprises poly(3,4-ethylenedioxythiophene).

22. The polymer film according to any one of claims 1 -21 , comprising one or more polymeric acid dopants.

23. The polymer film according to claim 22, wherein the one or more polymeric acid dopants comprise a water soluble polymeric acid dopant.

24. The polymer film according to claim 23, wherein the water soluble polymeric acid dopant comprises a poly(styrene sulfonic acid) dopant.

25. The polymer film according to any one of claims 1 -24, wherein the total transmittance is greater than or equal to 80%.

26. The polymer film according to any one of claims 1 -25, wherein the sheet resistance is from about 1 to about 30000 ohms per square.

27. A process for producing a polymer film according to any one of claims 1 -26, the process comprising:

(1 a) treating a pristine polymer film with at least one conductivity enhancing agent, or a solution thereof;

wherein the conductivity enhancing agent comprises a compound selected from the group consisting of alkane, cycloalkane, cyclic ether, cyclic ester, arene, heteroarene, and mixtures thereof; wherein when the conductivity enhancing agent comprises alkane, cycloalkane, cyclic ester, arene, and/or heteroarene, said alkane, cyclic ester, arene, and/or heteroarene are each substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl; and

wherein when the conductivity enhancing agent comprises a (CrC3)alkane, said (Ci-C3)alkane is substituted with at least two carboxy groups,

(2a) optionally washing the polymer film obtained in step (1 a), thereby producing the polymer film.

28. The process according to claim 27, wherein the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl.

29. The process according to claim 28, wherein the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

30. The process according to claim 29, wherein the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6-naphthalenedicarboxylic acid; 1 ,4- naphthalenedicarboxylic acid; or a mixture thereof.

31 . The process according to claim 28, wherein the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

32. The process according to claim 31 , wherein the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

33. The process according to claim 28, wherein the conductivity enhancing agent comprises a compound represented b the structure

wherein R_z is alkyl, hydroxy, carboxy, aroyl, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl; and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

34. The process according to claim 33, wherein R_z is alkyl, hydroxy, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

35. The process according to claim 34, wherein the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p-toluenesulfonic acid,

1 ,3,5-tris(4-carboxyphenyl)benzene, benzene-1 ,3, 5-th ace tic acid, or a mixture thereof.

36. The process according to claim 33, wherein R_z is carboxy, and R_a, Rb, R_c, Rd, R_e are each, independently, H, hydroxy, or carboxy.

37. The process according to claim 36, wherein the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 , 3, 5-tricarboxylic acid, or a mixture thereof.

38. The process according to claim 27, wherein the conductivity enhancing agent comprises a heteroarene substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

39. The process according to claim 38, wherein the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

40. The process according to claim 27, wherein the conductivity enhancing agent comprises a cycloalkane substituted with at least one carboxy group.

41 . The process according to claim 40, wherein the conductivity enhancing agent comprises 1 ,3,5-cyclohexanetricarboxylic acid.

42. The process according to claim 27, wherein the conductivity enhancing agent comprises an alkane substituted with at least one carboxy group.

43. The process according to claim 42, wherein the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6-hexanetricarboxylic acid; or a mixture thereof.

44. The process according to claim 27, wherein the conductivity enhancing agent comprises a cyclic ether.

45. The process according to claim 27, wherein the conductivity enhancing agent comprises a cyclic ester substituted with at least one hydroxyalkyl group.

46. The process according to any one of claims 27-45, wherein the pristine polymer film is treated with a solution comprising the at least one conductivity enhancing agent and a solvent.

47. The process according to claim 46, wherein the concentration of the at least one conductivity enhancing agent, based on 100 wt% of the solution, is from greater than 0 wt% to about 50 wt%.

48. The process according to claim 47, wherein the concentration of the at least one conductivity enhancing agent is from 0.01 wt% to about 30 wt%.

49. The process according to claim 48, wherein the concentration of the at least one conductivity enhancing agent is from 0.1 wt% to about 20 wt%.

50. A polymer composition comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants,

(c) at least one conductivity enhancing agent,

wherein when the conductivity enhancing agent comprises a (CrC₃)alkane, said (CrC₃)alkane is substituted with at least two carboxy groups; and

(d) a liquid medium.

51 . The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl.

52. The polymer composition according to claim 51 , wherein the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

53. The polymer composition according to claim 52, wherein the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6- naphthalenedicarboxylic acid; 1 ,4-naphthalenedicarboxylic acid; or a mixture thereof.

54. The polymer composition according to claim 51 , wherein the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

55. The polymer composition according to claim 54, wherein the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

56. The polymer composition according to claim 51 , wherein the conductivity enhancing agent comprises a com ound represented by the structure

wherein R_z is alkyl, hydroxy, carboxy, aroyl, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl; and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl.

57. The polymer composition according to claim 56, wherein R_z is alkyl, hydroxy, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyl, carboxyaryl, and carboxyalkyl.

58. The polymer composition according to claim 57, wherein the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p- toluenesulfonic acid, 1 ,3,5-tris(4-carboxyphenyl)benzene, benzene-1 ,3,5-triacetic acid, or a mixture thereof.

59. The polymer composition according to claim 56, wherein R_z is carboxy, and R_a, Rb, Rc, Rd, Re are each, independently, H, hydroxy, or carboxy.

60. The polymer composition according to claim 59, wherein the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, or a mixture thereof.

61 . The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises a heteroarene substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

62. The polymer composition according to claim 61 , wherein the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

63. The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises a cycloalkane substituted with at least one carboxy group.

64. The polymer composition according to claim 63, wherein the conductivity enhancing agent comprises 1 ,3,5-cyclohexanetricarboxylic acid.

65. The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises an alkane substituted with at least one carboxy group.

66. The polymer composition according to claim 65, wherein the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6- hexanetricarboxylic acid; or a mixture thereof.

67. The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises a cyclic ether.

68. The polymer composition according to claim 50, wherein the conductivity enhancing agent comprises a cyclic ester substituted with at least one hydroxyalkyi group.

69. The polymer composition according to any one of claims 50-68, comprising, based on 100 wt% of the polymer composition:

(a) from about 0.1 to about 10.0 wt% of electrically conductive polymer,

(b) from about 0 to about 10.0 wt% of polymeric acid dopant,

(c) from about 0.01 to about 70.0 wt% of conductivity enhancing agent,

(d) from about 1 .0 to about 99.0 wt% of liquid medium.

70. The polymer composition according to any one of claims 50-69, wherein the at least one electrically conductive polymer comprises at least one polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S.

71 . The polymer composition according to claim 70, wherein the at least one polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S, comprises poly(3,4-ethylenedioxythiophene).

72. The polymer composition according to any one of claims 50-71 , comprises one or more polymeric acid dopants, wherein the polymeric acid dopant is a water soluble polymeric acid dopant.

73. The polymer composition according to claim 72, wherein the water soluble polymeric acid dopant comprises a poly(styrene sulfonic acid) dopant.

74. A process for producing a polymer film, the process comprising:

(1 b) forming a layer of a polymer composition according to any one of claims 50-73,

(2b) removing the liquid medium from the layer,

thereby producing the polymer film.

75. The polymer film produced by the process according to claim 74.

76. A polymer complex comprising:

(a) at least one electrically conductive polymer,

(b) optionally one or more polymeric acid dopants, and

(c) at least one conductivity enhancing agent;

wherein when the conductivity enhancing agent comprises a (CrC₃)alkane, said (CrC₃)alkane is substituted with at least two carboxy groups.

77. The polymer complex of claim 76, wherein the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

78. The polymer complex of claim 77, wherein the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

79. The polymer complex of claim 78, wherein the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6-naphthalenedicarboxylic acid; 1 ,4- naphthalenedicarboxylic acid; or a mixture thereof.

80. The polymer complex of claim 77, wherein the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

81 . The polymer complex of claim 80, wherein the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

82. The polymer complex of claim 77, wherein the conductivity enhancing agent comprises a compound represented by the structure

83. The polymer complex of claim 82, wherein R_z is alkyl, hydroxy, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

84. The polymer complex of claim 83, wherein the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p-toluenesulfonic acid, 1 ,3,5-tris(4-carboxyphenyl)benzene, benzene-1 ,3,5-triacetic acid, or a mixture thereof.

85. The polymer complex of claim 82, wherein R_z is carboxy, and R_a, R_b, R_c, R_d, R_e are each, independently, H, hydroxy, or carboxy.

86. The polymer complex of claim 85, wherein the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, or a mixture thereof.

87. The polymer complex of claim 76, wherein the conductivity enhancing agent comprises a heteroarene substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

88. The polymer complex of claim 87, wherein the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

89. The polymer complex of claim 76, wherein the conductivity enhancing agent comprises a cycloalkane substituted with at least one carboxy group.

90. The polymer complex of claim 89, wherein the conductivity enhancing agent comprises 1 ,3,5-cyclohexanetricarboxylic acid.

91 . The polymer complex of claim 76, wherein the conductivity enhancing agent comprises an alkane substituted with at least one carboxy group.

92. The polymer complex of claim 91 , wherein the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6-hexanetricarboxylic acid; or a mixture thereof.

93. The polymer complex of claim 76, wherein the conductivity enhancing agent comprises a cyclic ether.

94. The polymer complex of claim claim 76, wherein the conductivity enhancing agent comprises a cyclic ester substituted with at least one hydroxyalkyl group.

95. The polymer complex according to any one of claims 76-94, wherein the at least one electrically conductive polymer comprises at least one polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S.

96. The polymer complex according to claim 95, wherein the at least one polythiophene polymer comprising monomeric units according to structure (I. a), wherein Q is S, comprises poly(3,4-ethylenedioxythiophene).

97. The polymer complex according to any one of claims 76-96, comprising one or more polymeric acid dopants.

98. The polymer complex according to claim 97, wherein the one or more polymeric acid dopants comprise a water soluble polymeric acid dopant.

99. The polymer complex according to claim 98, wherein the water soluble polymeric acid dopant comprises a poly(styrene sulfonic acid) dopant.

100. The polymer complex according to any one of claims 76-99, wherein the polymer complex is a polymer gel.

101 . The polymer complex according to any one of claims 76-99, wherein the polymer complex is a polymer foam.

102. A process for producing a polymer complex according to any one of claims 76-101 , the process comprising:

(1 c) treating a pristine polymer complex with at least one conductivity enhancing agent, or a solution thereof, wherein the conductivity enhancing agent comprises a compound selected from the group consisting of alkane, cycloalkane, cyclic ether, cyclic ester, arene, heteroarene, and mixtures thereof;

wherein when the conductivity enhancing agent comprises a (CrC₃)alkane, said (CrC₃)alkane is substituted with at least two carboxy groups;

(2c) optionally washing the polymer complex obtained in step (1 c), thereby producing the polymer complex.

103. The process according to claim 102, wherein the conductivity enhancing agent comprises an arene substituted with at least one substituent selected from the group consisting of alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

104. The process according to claim 103, wherein the conductivity enhancing agent comprises naphthalene substituted with at least one carboxy group.

105. The process according to claim 104, wherein the conductivity enhancing agent comprises naphthalene-2-carboxylic acid; 2,6-naphthalenedicarboxylic acid; 1 ,4-naphthalenedicarboxylic acid; or a mixture thereof.

106. The process according to claim 103, wherein the conductivity enhancing agent comprises anthracene substituted with at least one carboxy group.

107. The process according to claim 106, wherein the conductivity enhancing agent comprises anthracene-9-carboxylic acid, 2-anthracenecarboxylic acid, or a mixture thereof.

108. The process according to claim 103, wherein the conductivity enhancing agent comprises a compound represented b the structure

109. The process according to claim 108, wherein R_z is alkyl, hydroxy, aroyl, sulfonic acid, carboxyaryl, and carboxyalkyl, and R_a, Rb, R_c, Rd, Re are each, independently, H, alkyl, hydroxy, carboxy, aroyl, alkoxy, sulfonic acid, hydroxyalkyi, carboxyaryl, and carboxyalkyl.

1 10. The process according to claim 109, wherein the conductivity enhancing agent comprises toluene, phenol, benzophenone, oxybenzone, p-toluenesulfonic acid, 1 ,3,5-tris(4-carboxyphenyl)benzene, benzene-1 ,3, 5-triacetic acid, or a mixture thereof.

1 1 1 . The process according to claim 108, wherein R_z is carboxy, and R_a, Rb, Rc, Rd, R_e are each, independently, H, hydroxy, or carboxy.

1 12. The process according to claim 1 1 1 , wherein the conductivity enhancing agent comprises benzoic acid, salicylic acid, p-hydroxybenzoic acid, gentisic acid, gallic acid, terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, or a mixture thereof.

1 13. The process according to claim 102, wherein the conductivity enhancing agent comprises a heteroarene substituted with at least one substituent selected from the group consisting of hydroxyalkyl and carboxy.

1 14. The process according to claim 1 13, wherein the conductivity enhancing agent comprises furfuryl alcohol, 2-furoic acid, or a mixture thereof.

1 15. The process according to claim 102, wherein the conductivity enhancing agent comprises a cycloalkane substituted with at least one carboxy group.

1 16. The process according to claim 1 15, wherein the conductivity enhancing agent comprises 1 ,3,5-cyclohexanetricarboxylic acid.

1 17. The process according to claim 102, wherein the conductivity enhancing agent comprises an alkane substituted with at least one carboxy group.

1 18. The process according to claim 1 17, wherein the conductivity enhancing agent comprises heptanoic acid, citric acid, octane-1 ,8-dioic acid; 1 ,3,6- hexanetricarboxylic acid; or a mixture thereof.

1 19. The process according to claim 102, wherein the conductivity enhancing agent comprises a cyclic ether.

120. The process according to claim 102, wherein the conductivity enhancing agent comprises a cyclic ester substituted with at least one hydroxyalkyl group.

121 . The process according to any one of claims 102-120, wherein the pristine polymer film is treated with a solution comprising the at least one conductivity enhancing agent and a solvent.

122. The process according to claim 121 , wherein the concentration of the at least one conductivity enhancing agent, based on 100 wt% of the solution, is from greater than 0 wt% to about 50 wt%.

123. The process according to claim 122, wherein the concentration of the at least one conductivity enhancing agent is from 0.01 wt% to about 30 wt%.

124. The process according to claim 123, wherein the concentration of the at least one conductivity enhancing agent is from 0.1 wt% to about 20 wt%.

125. An electronic device, comprising:

(a) an anode layer,

(b) a cathode layer,

(c) an electroactive layer disposed between the anode layer and the

cathode layer,

(d) optionally, a buffer layer or hole injection layer,

(e) optionally, a hole transport layer, and

(f) optionally, an electron injection layer,

wherein at least one of the layers comprises a polymer film according to any one of claims 1 -26, or a polymer complex according to any one of claims 76-101 .

126. The electronic device of claim 125, wherein the anode layer comprises a combination of the anode layer and the buffer layer.

127. The electronic device of claim 125, wherein the device is a thermoelectric device.

128. The device of claim 127, wherein the device is a thermoelectric generator.

129. The device of claim 127, wherein the device is a thermoelectric cooler.

130. The electronic device of claim 125, wherein the device is a battery.

131 . The device of claim 130, wherein the battery has a rigid shape.

132. The device of claim 130, wherein the battery has a flexible, bendable, and/or twistable shape.

133. The electronic device of claim 125, wherein the device is a piezoresistive device.

134. The electronic device of claim 125, wherein the device is an electrochromic device.