US 2011 0315204A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0315204 A1 Gleason et al. (43) Pub. Date: Dec. 29, 2011

(54) CONDUCTIVE POLYMER ON A TEXTURED Publication Classification OR PLASTC SUBSTRATE (51) Int. Cl. HOIL 3L/02 (2006.01) (76) Inventors: Karen K. Gleason, Cambridge, HOIL 3L/18 (2006.01) MA (US); Vladimir Bulovic, HOIL 33/44 (2010.01) Lexington, MA (US); Miles C. (52) U.S. Cl...... 136/256; 257/98: 438/71; 438/29: Barr, Cambridge, MA (US); Jill A. 257/E33.067; 257/E31.13 Rowehl, Watertown, MA (US) (57) ABSTRACT (21) Appl. No.: 12/822,691 A conducting material can include a fibrous Substrate and a conductive polymer coating on a Surface of the fibrous Sub (22) Filed: Jun. 24, 2010 Strate.

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US 2011/03 15204 A1 Dec. 29, 2011

CONDUCTIVE POLYMER ON A TEXTURED can include poly(3,4-ethylenedioxythiophene). In some OR PLASTC SUBSTRATE embodiments, the polymer coating can include at least one dopant. TECHNICAL FIELD 0011. In some embodiments, the light absorbing or emit ting device can further include an electrode and an energy 0001. This invention relates to a conductive polymer coat converting region capable of converting energy between pho ing a surface of a textured or plastic Substrate. toenergy and electric energy. The energy converting region can be positioned between the electrode and the polymer BACKGROUND coating. 0012. In some embodiments, the polymer coating can be 0002 Conductive materials, such as conductive sub an anode and the electrode can be a cathode. strates, can be used to build structures with semiconductors to 0013 In some embodiments, the energy converting region create useful devices. Semiconductors are materials that can can include copper phthalocyanine, fullerene-Co or batho contain either an excess of free electrons (N-type) or “holes' cuprine. In some embodiments, the energy converting region (P-type). N- and P-type materials can be joined to form diodes can include poly(p-phenylene vinylene), polyfluorene, poly and transistors. Where the two films meet, negative charges (fluorenylene ethynylene), poly(phenylene ethynylene), can migrate across the junction to the positive side and vice polyfluorene vinylene, or polythiophene. In some embodi Versa, until an equilibrium is reached. This configuration can ments, the energy converting region can include at least one be used to create light emitting diodes (“LEDs) or photovol material selected from the group consisting of silicon, copper taic (“PV) structures. indium diselenide, Zinc oxide, Zinc sulfide, Zinc selenide, Zinc 0003. When a voltage is applied to an LED, a current flows telluride, cadmium oxide, cadmium Sulfide, cadmium through the junction in the form of electrons moving in one Selenide, cadmium telluride, magnesium oxide, magnesium direction while holes move in the other direction. The migra Sulfide, magnesium selenide, magnesium telluride, mercuric tion of ionic charge across the junction causes a higher elec oxide, mercuric sulfide, mercuric selenide, mercuric tellu trical potential than normal, which affects the way electrons ride, aluminum nitride, aluminum phosphide, aluminum ars combine with holes. When an electron combines with a hole, enide, aluminum antimonide, gallium nitride, gallium phos it can form an excited State pair, called an exciton, which can phide, gallium arsenide, gallium antimonide, indium nitride, quickly release the energy as photons of light. Conversely, indium phosphide, indium arsenide, indium antimonide, thal when a light of an appropriate wavelength is applied to a lium nitride, thallium phosphide, thallium arsenide, thallium photovoltaic structure, photons are absorbed by the mol antimonide, lead sulfide, lead selenide, or lead telluride. ecules, form excitons. The charges of the exciton can sepa 0014. In some embodiments, the light absorbing device rate, moving toward opposite electrodes, thereby establishing can be a photovoltaic. In other embodiments, the light emit a Current. ting device can be a light emitting diode. 0015. In another aspect, a light absorbing device can SUMMARY include a plastic Substrate and a conductive polymer coating on a surface of the Substrate. In some embodiments, the 0004 Semiconductors on common fiber-based papers and substrate can be flexible. ultrathin plastics can be lightweight and foldable for storage 0016. In some embodiments, the surface of the substrate and portability, easily shaped for three-dimensional applica can include a plurality of functional groups. The conductive tions, cut to size with Scissors or tornby hand, and compatible polymer can interact with the plurality of functional groups. with roll-to-roll manufacturing. However, such Substrates can The conductive polymer can form a covalent bond with the be easily damaged by common processing agents such as plurality of functional groups. Solvents, plasmas, or heat. Advantageously, a conductive 0017. In some embodiments, the polymer coating can polymer coating can be deposited on a Substrate that can include monomeric units derived from optionally substituted include a textured Surface. thiophenes, optionally Substituted pyrroles or optionally Sub 0005. In one aspect, a light absorbing or emitting device stituted anilines. The polymer coating can include poly(3,4- can include a Substrate with a textured Surface and a conduc ethylenedioxythiophene). The polymer coating can include at tive polymer coating on a surface of the Substrate. least one dopant. 0006. In another aspect, a method of making a light 0018. In some embodiments, the light absorbing device absorbing or light emitting device can include providing a can further include an electrode and an energy converting plastic or textured Substrate including a conductive polymer region capable of converting energy between photoenergy on a Surface of the Substrate and depositing an energy con and electric energy. Verting region capable of converting energy between photo 0019. In some embodiments, the polymer coating can be energy and electric energy on the Substrate. an anode and the electrode can be a cathode. 0007. In some embodiments, the textured surface can be 0020. In some embodiments, the energy converting region porous or fibrous. In certain circumstances, the Substrate can can include copper phthalocyanine, fullerene-Co or batho be paper or cloth. cuprine. In some embodiments, the energy converting region 0008. In some embodiments, the substrate can be flexible. can include poly(p-phenylene vinylene), polyfluorene, poly 0009. In some embodiments, the polymer coating can be (fluorenylene ethynylene), poly(phenylene ethynylene), conformal to the surface of the substrate. polyfluorene vinylene, or polythiophene. In some embodi 0010. In some embodiments, the polymer coating can ments, the energy converting region can include at least one include monomeric units derived from optionally substituted material selected from the group consisting of silicon, copper thiophenes, optionally Substituted pyrroles or optionally Sub indium diselenide, Zinc oxide, Zinc sulfide, Zinc selenide, Zinc stituted anilines. In some circumstances, the polymer coating telluride, cadmium oxide, cadmium Sulfide, cadmium US 2011/03 15204 A1 Dec. 29, 2011

Selenide, cadmium telluride, magnesium oxide, magnesium 0043 FIG. 9 illustrates exemplary configurations includ Sulfide, magnesium selenide, magnesium telluride, mercuric ing a conducting material. oxide, mercuric sulfide, mercuric selenide, mercuric tellu ride, aluminum nitride, aluminum phosphide, aluminum ars DETAILED DESCRIPTION enide, aluminum antimonide, gallium nitride, gallium phos 0044) There is a need for development of conducting poly phide, gallium arsenide, gallium antimonide, indium nitride, mers deposited directly on Substrates that are inexpensive, indium phosphide, indium arsenide, indium antimonide, thal widely available, and compatible with high-throughput lium nitride, thallium phosphide, thallium arsenide, thallium manufacturing. In addition, conducting polymers, for antimonide, lead sulfide, lead selenide, or lead telluride. example in photovoltaics, on common paper, plastic, or fiber 0021. In some embodiments, the light absorbing device Substrates could be seamlessly integrated into existing prod can be a photovoltaic. ucts (e.g. wall paper, window curtains, newspapers, clothing, 0022. Other embodiments are within the claims. etc.). Existing synthesis techniques for conducting polymers BRIEF DESCRIPTION OF THE DRAWINGS can preclude their deposition on Some Substrates like paperor on top of other materials that are incompatible with solutions 0023 FIG. 1a is a schematic of the oxidative chemical based processing. This fact can limit their application in elec vapor deposition (“oCVD). tronic devices, such as photovoltaics (“PVs) or light emitting 0024 FIG. 1b is a picture of poly(3,4-ethylenediox diodes (“LEDs), as a bottom-electrode layer or as a coating ythiophene) (“PEDOT) applied to SARANTM wrap by two on a bottom electrode to facilitate better hole injection. For deposition techniques. example, conventional transparent electrodes (e.g. indium tin 0025 FIG.2a is a graph demonstrating the current-voltage oxide) can be deposited via sputtering, which is not compat (“J-V) characteristics for OCVD PEDOT-based organic pho ible with processing-sensitive substrates. Progress has been tovoltaics (“OPVs) and conventional indium tin oxide made in the development of Solution-processable materials (ITO) based OPVs on rigid glass substrates. for large-area printing of flexible photovoltaics; however, 0026 FIG.2b is a graph showing the effect of oCVD film solution wettability and solvent compatibility requirements thickness on transmittance and inverse sheet resistance. can limit substrate choices. The development of a robust 0027 FIG. 3a is a graph demonstrating the conductivity vapor-deposition technique for conducting polymers that pre with respect to flexing cycle for OCVD PEDOT film serves their high conductivity and is compatible with mois covalently bonded to a flexible polyethylene terephthalate ture-sensitive, temperature-sensitive, and mechanically frag (“PET) substrate and ITO-coated PET. ile surfaces is needed to broaden their utilization, enabling 0028 FIG.3b is a graph showing the J-V characteristics of both improved efficiencies in existing devices and develop an ITO-free OPV on PET before and after flexing cycles. ment of new devices on unconventional Substrates. 0029 FIG.3c is a graph demonstrating the conductivity of 0045. In 1977, the field of conducting polymeric materi anoCVD PEDOT electrode on SARANTM wrap as it is aniso als, also known as synthetic metals, began with the discovery tropically stretched until substrate failure. that polyacetylene conducts electricity. (H. Shirakawa, E. J. 0030 FIG.3d is a graph demonstrating the conductivity of Louis, A. G. Macdiamid, C. K. Chiang, and A. J. Heeger, an oCVD PEDOT electrode on newsprint after repeated fold “Synthesis of Electrically Conducting Organic Polymers— ing. Halogen Derivatives of Polyacetylene, (Ch)X.” Journal of the 0031 FIG. 4a is a graph showing the J-V performance Chemical Society-Chemical Communications 16, 578-580 characteristics of OPVs utilizing oCVD PEDOT electrodes (1977), which is incorporated by reference in its entirety). on tracing paper (FIG.4b), tissue paper (FIG. 4c), and printed Efforts to incorporate conducting polymers into electronic paper (FIG. 4d). devices, including light-emitting diodes (LEDs), electrochro 0032 FIG. 4e shows a paper airplane with integrated pho mic materials and structures, microelectronics, portable and tovoltaic wings folded from a sheet of tracing paper patterned large-area displays, and photovoltaics have continued since with an oCVD-enabled device. that time. (C. T. Chen, “Evolution of red organic light-emit 0033 FIG. 4f shows printed newspaper with an oGVD ting diodes: Materials and devices.” Chemistry of Materials enabled device. 16(23), 4389-4400 (2004); A. P. Kulkarni, C.J. Tonzola, A. 0034 FIG. 4g shows wax paper with an OCVD-enabled Babel, and S. A. Jenekhe, “Electron transport materials for device. organic light-emitting diodes. Chemistry of Materials 0035 FIG. 5a shows an oCVD polymer electrode on a 16(23), 4556-4573 (2004); A. A. Argun, P. H. Aubert, B. C. single ply of bathroom tissue. Thompson, I. Schwendeman, C. L. Gaupp, J. Hwang, N. J. 0036 FIG. 5b shows a single ply of bathroom tissue Pinto, D. B. Tanner, A. G. MacDiamid, and J. R. Reynolds, exposed to a drop-cast conducting polymer Solution. “Multicolored electrochromism polymers: Structures and 0037 FIG. 5c shows a measurement of the 2-point film devices.” Chemistry of Materials 16(23), 4401-4412 (2004); resistance of an oGVD PEDOT electrode on a single ply of D. K. James and J. M. Tour, "Electrical measurements in bathroom tissue. molecular electronics.” Chemistry of Materials 16(23), 4423 0038 FIG. 6a shows rice paper with an OCVD polymer 4435 (2004); C. R. Newman, C. D. Frisbie, D.A. da Silva, J. electrode. L. Bredas, P. C. Ewbank, and K. R. Mann, “Introduction to 0039 FIG. 6b shows rice paper after being exposed to a organic thin film transistors and design of n-channel organic drop-cast conducting polymer. semiconductors. Chemistry of Materials 16(23), 4436-4451 0040 FIG. 6c shows a measurement of the 2-point film (2004); M. L. Chabinyc and A. Salleo, “Materials require resistance of an oGVD PEDOT electrode on rice paper. ments and fabrication of active matrix arrays of organic thin 0041 FIG. 7 shows a conductive polymer conforming to film transistors for displays.” Chemistry of Materials 16(23), fibers of substrates. 4509-4521 (2004); and K. M. Coakley and M. D. McGehee, 0042 FIG. 8 shows the oCVD system. “Conjugated polymer photovoltaic cells. Chemistry of US 2011/03 15204 A1 Dec. 29, 2011

Materials 16(23), 4533-4542 (2004), each of which is incor by a change of solvents. Synthetic Metals 126(2-3), 311-316 porated by reference in its entirety.) (2002), each of which is incorporated by reference in its 0046 Polymers, such as polyphenylene, polyaniline, entirety.) Bayer's first major customer for BATRON P was polythiophene, polypyrrole, polycarbazole, or polysilane, Agfa who used the material as an anti-static coating on pho can have delocalized electrons along their backbones tographic film. (F. Jonas, W. Kraffi, and B. Muys, “Poly(3,4- enabling charge conduction. The conductivity can increase Ethylenedioxythiophene)-Conductive Coatings, Technical when anions present as dopants in the polymer matrix stabi Applications and Properties.” Macromolecular Symposia lize positive charges along the chain. Each of the conducting 100, 169-173 (1995); Bayer, European Pat 440957 (1991); polymers can be substituted with a variety of functional and Agfa, European Patent 564911 (1993), each of which is groups to achieve different properties, so new derivatives incorporated by reference in its entirety.) Any spark generated continue to be synthesized. (J. L. Bredas and R. J. Silbey, by static electricity can expose film showing up as a bright Conjugated polymers: the novel Science and technology of spot on developed photos. Bayer has since enjoyed utilization highly conducting and nonlinear optically active materials of BAYTRONP as an electrode material in capacitors and a (Kluwer Academic Publishers, Dordrecht; Boston, 1991), pp. material for through-hole plating of printed circuit boards. (F. xviii. 624 p.; and T. A. Skotheim, R. L. Elsenbaumer, and J. R. Jonas and J. T. Morrison, "3,4-polyethylenedioxythiophene Reynolds, Handbook of conducting polymers, 2nd ed. (M. (PEDT): Conductive coatings technical applications and Dekker, New York, 1998), pp. xiii. p. 1097, each of which is properties. Synthetic Metals 85(1-3), 1397-1398 (1997); incorporated by reference in its entirety.) Bayer, European Patent 533671 (1993); Bayer, European 0047 One conducting polymer can be poly-3,4-ethylene Patent 686662 (1995); Bayer, U.S. Pat. No. 5,792,558 (1996): dioxy-thiophene (PEDOT) developed by scientists at Bayer and F. Jonas and G. Heywang, “Technical Applications for AG in Germany. (Bayer, Eur. Patent 339340 (1988); B. L. Conductive Polymers.” Electrochimica Acta 39(8-9), 1345 Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. 1347 (1994), each of which is incorporated by reference in its Reynolds, “Poly(3,4-ethylenedioxythiophene) and its deriva entirety.) BAYTRON P can also be suitable as a hole-inject tives: Past, present, and future.” Advanced Materials 12(7), ing layer in LEDs and photovoltaics, increasing device effi 481-494 (2000); and F. Jonas and L. Schrader, “Conductive ciency by up to 50%. (T. M. Brown, J. S. Kim, R. H. Friend, Modifications of Polymers with Polypyrroles and Poly F. Cacialli, R. Daik, and W. J. Feast, "Built-in field electro thiophenes.” Synthetic Metals 41(3), 831-836 (1991), each of absorption spectroscopy of polymer light-emitting diodes which is incorporated by reference in its entirety.) It was incorporating a doped poly(3,4-ethylene dioxythiophene) initially designed to block the B-positions on the thiophene hole injection layer.” Applied Physics Letters 75(12), 1679 ring to prevent undesirable side reactions. The strategy 1681 (1999); and G. Greczynski, T. Kugler, M. Keil, W. worked and the ethylene bridge on the molecule can act as a Osilkowicz, M. Fahlman, and W. R. Salaneck, “Photoelectron good charge donor to the TL-conjugated backbone, giving rise spectroscopy of thin films of PEDOT:PSS conjugated poly to an unusually high conductivity of 300 S/cm. (G. Heywang mer blend: a mini-review and some new results.” Journal of and F. Jonas, “Poly(Alkylenedioxythiophene)S New, Very Electron Spectroscopy and Related Phenomena 121(1-3), Stable Conducting Polymers. Advanced Materials 4(2), 116 1-17 (2001), each of which is incorporated by reference in its 118 (1992), which is incorporated by reference in its entirety.) entirety). In addition, PEDOT films in their oxidized state can 0048 Conducting polymer materials can be formed via be extremely stable for conducting polymers and nearly oxidative polymerization of aniline, pyrrole, thiophene, or transparent. (M. Dietrich, J. Heinze, G. Heywang, and F. their derivatives. (A. Malinauskas, “Chemical deposition of Jonas, “Electrochemical and Spectroscopic Characterization conducting polymers.” Polymer 42(9), 3957-3972 (2001), of Polyalkylenedioxythiophenes.” Journal of Electroanalyti which is incorporated by reference in its entirety). In general, cal Chemistry 369(1-2), 87-92 (1994), which is incorporated it has not been feasible to process bulk material of these by reference in its entirety). However, like other conjugated polymers into thin films since they can be insoluble and polymers that have a very rigid conformation in order to non-melting, but coating techniques have been developed on maintain electron orbital overlap along the backbone, Substrates including plastic, glass, metal, fabric and micro PEDOT can be insoluble. Bayer addressed this problem by and nano-particles. Four main approaches can be utilized to using a water soluble polyanion, polystyrene Sulfonic acid form coatings of anilines, pyrroles, or thiophenes via Oxida (PSS), during polymerization as the charge-balancing tive polymerization on various materials: electropolymeriza dopant. The PEDOT:PSS system is marketed as BAYTRON tion of monomers at electrodes, casting a solution of mono PTM and it has good film forming capabilities, a conductivity mer and oxidant on a surface and allowing the solvent to of 10 S/cm, good transparency, and extremely good stability. evaporate, immersing a substrate in a solution of monomer In fact, the films can be heated in air over 100° C. for over and oxidant during polymerization, and chemical oxidation 1000 hours with no major decline in conductivity. Studies of a monomer directly on a Substrate surface that has been demonstrate that Bayer's BAYTRON P materials (PEDOT enriched with an oxidant. stabilized with polystyrene sulfonate) can have increased 0049. Historically, electrochemical oxidation on different conductivity up to 600 S/cm by adding N-methyl-pyrolidone electrode materials has been the primary route to conducting (NMP) or other solvents that reduce screening effects of the polyaniline, polypyrrole films, polythiophene, and their polar solvent between the dopant and the polymer main chain. derivatives. (E. M. Genies, A. Boyle, M. Lapkowski, and C. (F. Louwet, L. Groenendaal, J. Dhaen, J. Manca, J. Van Lup Tsintavis, “Polyaniline—a Historical Survey. Synthetic pen, E. Verdonck, and L. Leenders, “PEDOT/PSS: synthesis, Metals 36(2), 139-182 (1990); L. X. Wang, X. G. Li, andY. L. characterization, properties and applications. Synthetic Met Yang, "Preparation, properties and applications of polypyr als 135(1-3), 115-117 (2003); and J.Y. Kim, J. H. Jung, D. E. roles.” Reactive & Functional Polymers 47(2), 125-139 Lee, and J. Joo, “Enhancement of electrical conductivity of (2001); E. Smela, “Microfabrication of PPy microactuators poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) and other conjugated polymer devices.” Journal of Microme US 2011/03 15204 A1 Dec. 29, 2011 chanics and Microengineering 9(1), 1-18 (1999); Q. B. Pei, poly(3,4-ethylenedioxythiophene) and its spectroscopic G. Zuccarello, M. Ahlskog, and O. Inganas, “Electrochromic data.” Synthetic Metals 100(2), 237-239 (1999); F. Tran-Van, and Highly Stable Poly(3,4-Ethylenedioxythiophene) S. Garreau, G. Louarn, G. Froyer, and C. Chevrot, “Fully Switches between Opaque Blue-Black and Transparent Sky undoped and soluble oligo(3,4-ethylenedioxythiophene)S: Blue.” Polymer 35(7), 1347-1351 (1994): R. Kiebooms, A. spectroscopic study and electrochemical characterization.” Aleshin, K. Hutchison, and F. Wudl, “Thermal and electro Journal of Materials Chemistry 11(5), 1378-1382 (2001); D. magnetic behavior of doped poly(3,4-ethylenediox Hohnholz, A. G. MacDiamid, D. M. Sarno, and W. E. Jones, ythiophene) films,” Journal of Physical Chemistry B 101 (51), “Uniform thin films of poly-3,4-ethylenedioxythiophene 11037-11039 (1997); A. M. White and R. C.T. Slade, “Elec (PEDOT) prepared by in-situ deposition.” Chemical Commu trochemically and vapour grown electrode coatings of poly nications (23), 2444-2445 (2001); A. Pron, F. Genoud, C. (3,4-ethylenedioxythiophene) doped with heteropolyacids.” Menardo, and M. Nechtschein, “The Effect of the Oxidation Electrochimica Acta 49(6), 861-865 (2004); and A. Aleshin, Conditions on the Chemical Polymerization of Polyaniline.” R. Kiebooms, R. Menon, F.Wudl, and A.J. Heeger, "Metallic Synthetic Metals 24(3), 193-201 (1988); M. Angelopoulos, conductivity at low temperatures in poly(3,4-ethylenediox G. E. Asturias, S. P. Ermer, A. Ray, E. M. Scherr, A. G. ythiophene) doped with PF6, Physical Review B 56(7), Macdiamid, M. Akhtar, Z. Kiss, and A. J. Epstein, “Polya 3659-3663 (1997), each of which is incorporated by reference niline—Solutions, Films and Oxidation-State. Molecular in its entirety.) Deposition can take place on an inert electrode Crystals and Liquid Crystals 160, 151-163 (1988);Y. Cao, A. material, which can be platinum, but can also be iron, copper, Andreatta, A.J. Heeger, and P. Smith, “Influence of Chemical Zinc, chrome-gold, lead, palladium, different types of carbon, Polymerization Conditions on the Properties of Polyaniline.” semiconductors, or on transparent electrodes like indium tin Polymer 30(12), 2305-2311 (1989); J. C. Chiang and A. G. oxide. (D. W. Deberry, “Modification of the Electrochemical Macdiamid, “Polyaniline Protonic Acid Doping of the and Corrosion Behavior of Stainless-Steels with an Electro Emeraldine Form to the Metallic Regime. Synthetic Metals active Coating.” Journal of the Electrochemical Society 132 13(1-3), 193-205 (1986); and I. Kogan, L. Folkeeva, I. (5), 1022-1026 (1985); G. Mengoli, M. M. Musiani, B. Pelli, Shunina, Y. Estrin, L. Kasumova, M. Kaplunov, G. Davidova, and E. Vecchi, "Anodic Synthesis of Sulfur-Bridged Polya and E. Knerelman, “An oxidizing agent for aniline polymer niline Coatings onto Fe Sheets.” Journal of Applied Polymer ization.” Synthetic Metals 100(3), 303-303 (1999), each of Science 28(3), 1125-1136 (1983); and G. Mengoli, M. T. which is incorporated by reference in its entirety.) Munari, and C. Folonari, "Anodic Formation of Polynitroa 0051. The presence of the strongest of the acid anions nilide Films onto Copper,” Journal of Electroanalytical (e.g., chloride) in the oxidant can result in the highest con Chemistry 124(1-2), 237-246 (1981), each of which is incor ductivities. Chemical oxidation can produce polymers with porated by reference in its entirety). Electrochemical oxida conductivities comparable to electrochemically deposited tion can take place in an acidic electrolytic solution having films using the same oxidant. (J. A. Walker, L. F. Warren, and anions like chloride, Sulfate, fluorosulfonates, and hexafluo E. F. Witucki, “New Chemically Prepared Conducting Pyr rophosphate. Deposition can occur as the potential of the role Blacks.” Journal of Polymer Science Part a-Polymer electrode is cycled in a range of around -0.6V to 1 V. Aniline Chemistry 26(5), 1285-1294 (1988), which is incorporated and pyrrole polymerized electrochemically can have conduc by reference in its entirety.) Generally, polar solvents like tivities ranging as high as 10 S/cm. Electrochemically depos alcohols or acetonitrile can be used and reactions can take ited polythiophenes, especially the PEDOT derivative, can place over a range of oxidant concentrations and temperatures reach conductivities that are an order of magnitude higher, including 0 to 80°C., under acidic or basic conditions. (L.Yu. around 200 to 300 S/cm. (H. Yamato, K. Kai, M. Ohwa, T. M. Borredon, M. Jozefowicz, G. Belorgey, and R. Buvet, Asakura, T. Koshiba, and W. Wernet, “Synthesis of free Journal of Polymer Science Part A-Polymer Chemistry 10, standing poly(3,4-ethylenedioxythiophene) conducting 2931 (1987), which is incorporated by reference in its polymer films on a pilot scale. Synthetic Metals 83(2), 125 entirety). However, these parameters can influence the yield 130 (1996), which is incorporated by reference in its entirety.) of polymerization and the conductivity of the final product. Using a variety of heteropolyacids as dopants in the electro Solution-based chemical oxidation can produce powder pre lyte solution can enable the formation of free-standing films cipitates that are packed into the form of a tablet and then as opposed to coatings on electrodes. Although electrochemi characterized since they are generally insoluble and do not cal polymerization can produce films that may not be pro melt. The polymerized material can be rinsed in water, metha cessable, it can have an advantage of making a clean product nol, or acetonitrile to remove unreacted oxidant. Improved that does not need to be extracted from a solution. The experi conductivities can be obtained after rinsing the material in a mental setup can also be coupled to physical spectroscopic Solution containing anionic dopants like hydrochloric acid techniques like visible, IR, Raman, and ellipsometry for in (HCl) or dissolved nitrosonium hexafluorophosphate situ characterization. (NOPF). Chemical polymerization of aniline or pyrrole can 0050 Chemical oxidation of unsubstituted or substituted result in conductivities as high as 10 or 50 S/cm, although aniline, pyrrole, or thiophene can also take place in Solution in using TBAP was reported to give polyaniline with a conduc the presence of an oxidant, for example, iron(III) chloride, tivity of 400 S/cm. PEDOT can often have a conductivity of iron(III) tosylate, hydrogen peroxide, potassium iodate, up to 200 or 300 S/cm. A film with these materials can be potassium chromate, ammonium sulfate, or tetrabutylammo formed by immersing a Substrate in the reaction Solution nium persulfate (TBAP). (A. Yasuda and T. Shimidzu, during polymerization. “Chemical Oxidative Polymerization of Aniline with Ferric 0.052 Polyaniline can also be synthesized via the Ullmann Chloride.” Polymer Journal 25(4), 329-338 (1993); R. Cor reaction using p-bromoaniline as a precursor, but a low con radi and S. P. Armes, “Chemical synthesis of poly(3,4-ethyl ductivity of only 10 S/cm was measured. (F. Ullmann, Ber enedioxythiophene). Synthetic Metals 84(1-3), 453-454 Dtsch Chem Ges 36, 2382-2384 (1903), which is incorpo (1997); T. Yamamoto and M. Abla, “Synthesis of non-doped rated by reference in its entirety). Interfacial polymerization US 2011/03 15204 A1 Dec. 29, 2011 of pyrrole using an aqueous oxidant solution and an organic scope,” Journal of Applied Physics 80(1), 70-75 (1996); and phase with dissolved monomer can achieve free-standing thin P. Bruschi, F. Cacialli, A. Nannini, and B. Neri, "Low-Fre films with conductivities of as high as 50 S/cm. (M. Nakata, quency Resistance Fluctuation Measurements on Conducting M. Taga, and H. Kise, “Synthesis of Electrical Conductive Polymer Thin-Film Resistors.” Journal of Applied Physics Polypyrrole Films by Interphase Oxidative Polymerization— 76(6), 3640-3644 (1994), each of which is incorporated by Effects of Polymerization Temperature and Oxidizing reference in its entirety.) Agents. Polymer Journal 24(5), 437-441 (1992), which is 0055 Vacuum deposition of polyaniline films using incorporated by reference in its entirety.) evaporation can yield conductivities of about 10 S/cm. (T. 0053 Dipping a substrate material into a solution contain L. Porter, K. Caple, and G. Caple, "Structure of Chemically ing oxidants like FeCls or Fe(OTs) and allowing it to dry can Prepared Freestanding and Vacuum-Evaporated Polyaniline yield an oxidant-enriched substrate that can provide a reactive Thin-Films.” Journal of Vacuum Science & Technology Surface that polymerizes Volatile monomers including a-Vacuum Surfaces and Films 12(4), 2441-2445 (1994); and aniline, pyrrole, thiophene, or their derivatives. (B. Winther T. R. Dillingham, D. M. Cornelison, and E. Bullock, “Inves Jensen, J. Chen, K. West, and G. Wallace, "Vapor phase tigation of Vapor-Deposited Polyaniline Thin-Films.” Journal polymerization of pyrrole and thiophene using iron(III) sul of Vacuum Science & Technology a-Vacuum Surfaces and fonates as oxidizing agents.” Macromolecules 37(16), 5930 Films 12(4), 2436-2440 (1994), each of which is incorporated 5935 (2004); J. Kim, E. Kim, Y. Won, H. Lee, and K. Suh, by reference in its entirety.) Solid polyaniline can be sublimed “The preparation and characteristics of conductive poly(3,4- attemperatures of about 400° C. and pressures of 10 or 10 ethylenedioxythiophene) thin film by vapor-phase polymer Torr. Compositional analysis using XPS can show a carbon ization.” Synthetic Metals 139(2), 485-489 (2003); and B. to-nitrogen ratio of about 6:1 for the source material. A Winther-Jensen and K. West, "Vapor-phase polymerization slightly higher C/N ratio in the deposited film can indicate of 3,4-ethylenedioxythiophene: A route to highly conducting that short oligomers preferentially sublime. polymer surface layers.” Macromolecules 37(12), 4538-4543 0056 Plasma-enhanced chemical vapor deposition (2004), each of which is incorporated by reference in it (PECVD) can be another method of depositing aniline, entirety.) A conductivity of 50 S/cm can be achieved using thiophene or parylene-substituted precursors. However, this method for polypyrrole and 500 to 1000 S/cm has been PECVD can yield low conductivities of only 10 S/cm due to reported for PEDOT. Oxidant pretreatment can be extended ring breakage or other imperfections caused by the high ener to glass Substrates, polymers, fabrics, and even individual gies inherent with plasma. (C.J. Mathai, S. Saravanan, M. R. fibers. (S. N. Tan and H. L. Ge. “Investigation into vapour Anantharaman, S. Venkitachalam, and S. Jayalekshmi, phase formation of polypyrrole. Polymer 37(6), 965-968 “Characterization of low dielectric constant polyaniline thin (1996); A. Mohammadi, I. Lundstrom, and O. Inganas, “Syn film synthesized by ac plasma polymerization technique.” thesis of Conducting Polypyrrole on a Polymeric Template.” Journal of Physics D-Applied Physics 35(3), 240-245 (2002); Synthetic Metals 41(1-2), 381-384 (1991); and C. C. Xu, P. K. Tanaka, K. Yoshizawa, T. Takeuchi, T. Yamabe, and J. Wang, and X. T. Bi, “Continuous Vapor-Phase Polymeriza Yamauchi, “Plasma Polymerization of Thiophene and 3-Me tion of Pyrrole. 1. Electrically Conductive Composite Fiber of thylthiophene.” Synthetic Metals 38(1), 107-116 (1990). L. Polypyrrole with Poly(P-Phenylene Terephthalamide). Jour M. H. Groenewoud, G. H. M. Engbers, R. White, and J. nal of Applied Polymer Science 58(12), 2155-2159 (1995). Feijen, "On the iodine doping process of plasma polymerised Pretreatinga Surface with iodine vapors can present a solvent thiophene layers.” Synthetic Metals 125(3), 429-440 (2001): less polymerization process for polypyrrole, but only low and L. M. H. Groenewoud, A. E. Weinbeck, G. H. M. Eng conductivities ranging from 10. Sup.-7 to 10. Sup.-1 S/cm bers, and J. Feijen, “Effect of dopants on the transparency and result. S. L. Shenoy, D. Cohen, C. Erkey, and R. A. Weiss, “A stability of the conductivity of plasma polymerised thiophene Solvent-free process for preparing conductive elastomers by layers.” Synthetic Metals 126(2-3), 143-149 (2002), each of an in situ polymerization of pyrrole.” Industrial & Engineer which is incorporated by reference in its entirety.) Another ing Chemistry Research 41(6), 1484-1488 (2002), each of conjugated monomer, 3.4.9,10-perylenetetracarboxylic dian which is incorporated by reference in its entirety.) hydride (PTCDA), can fare much better using PECVD, with 0054 Another solvent-less deposition process has been reported conductivities as high as 50 S/cm. (M. Murashima, demonstrated for polypyrrole that eliminates the step of dip K. Tanaka, and T. Yamabe, “Electrical-Conductivity of coating a substrate in an oxidant solution, although it can be Plasma-Polymerized Organic Thin-Films—Influence of restricted to metallic substrates. The surface of metals includ Plasma Polymerization Conditions and Surface-Composi ing copper, iron, gold, and/or palladium can be converted into tion.” Synthetic Metals 33(3), 373-380 (1989), which is salts by exposing them to vapors of chlorine, iodine, or bro incorporated by reference in its entirety.) mine and acids with F, NO, SO, or CIO, anions. Sub 0057 Thermally activated hot-wire CVD can be used to sequent introduction of monomer vapor can result in polymer polymerize aniline or vinyl-containing monomers, including films with conductivities of around 1 to 10 S/cm. (G. Serra, R. phenylenevinylene or vinylcarbazole, but no conductivities Stella, and D. De Rossi, “Study of the influence of oxidising of these materials have been reported. (G. A. Zaharias, H. H. salt on conducting polymer sensor properties.” Materials Sci Shi, and S. F. Bent, "HotWire Chemical Vapor Deposition as ence & Engineering C-Biomimetic Materials Sensors and a Novel Synthetic Method for Electroactive Organic Thin Systems 5(3-4), 259-263 (1998); A. Nannini and G. Serra, Films.” Mat. Res. Soc. Symp. Proc. 814, I12.19.11-I12.19.16 “Growth of Polypyrrole in a Pattern—a Technological (2004); K. M. Vaeth and K. F. Jensen, “Chemical vapor depo Approach to Conducting Polymers.” Journal of Molecular sition of thin polymer films used is polymer-based light emit Electronics 6(2), 81-88 (1990); F. Cacialli and P. Bruschi, ting diodes.” Advanced Materials 9(6), 490-& (1997); K. M. “Site-selective chemical-vapor-deposition of submicron Vaeth and K. F. Jensen, “Transition metals for selective wide conducting polypyrrole films: Morphological investiga chemical vapor deposition of parylene-based polymers.” tions with the scanning electron and the atomic force micro Chemistry of Materials 12(5), 1305-1313 (2000); and M. US 2011/03 15204 A1 Dec. 29, 2011

Tamada, H. Omichi, and N. Okui, "Preparation of polyvinyl can make the coating Solution acidic. This fact can lead to carbazole thin film with vapor deposition polymerization.” different film forming characteristics depending on the ability Thin Solid Films 268(1-2), 18-21 (1995), each of which is of the Solution to wet different materials like glass, plastic, or other active layers in a device. In addition, some devices incorporated by reference it its entirety.) Photo-induced CVD simply cannot be compatible with wet processing techniques. can be used to couple thiophene monomers that were halo 0060. Therefore, the development of a robust vapor-depo genated with bromine orchlorine at the 2- and 5-positions. (T. sition technique for PEDOT films could simplify the coating Sorita, H. Fujioka, M.Inoue, and H. Nakajima, “Formation of process on a variety of organic and inorganic materials since Polymerized Thiophene Films by Photochemical Vapor it would not depend on evenly wetting the substrate surface. Deposition.” Thin Solid Films 177,295-303 (1989), which is Vapor-phase deposition could also provide uniform coatings incorporated by reference in its entirety.) Although the mono on Substrates with high Surface areas due to roughness or mers may couple at the halogenated positions, only relatively fibrous and porous morphologies. Increasing the effective low conductivities of 10 S/cm can be achieved. However, Surface area of devices can improve operating efficiencies and dibrominated PEDOT can polymerize upon heating and coating unconventional Surfaces like paper, fabric, or Small makes films with a conductivity of 20 S/cm. (H. Meng, D. F. particles can lead to the innovation of new devices. Vapor Perepichka, M. Bendikov, F. Wudl, G. Z. Pan, W.J. Yu, W.J. phase techniques using oxidant-enriched substrates which Dong, and S. Brown, “Solid-state synthesis of a conducting have been coated with solutions of Fe(III) tosylate and polythiophene via an unprecedented heterocyclic coupling allowed to dry have been developed. Exposing the treated reaction.” Journal of the American Chemical Society 125 surface to EDOT vapors can result in the polymerization of (49), 15151-15162 (2003), which is incorporated by refer films with conductivities reported to be as high as 1000 S/cm. ence in its entirety.) (J. Kim, E. Kim, Y. Won, H. Lee, K. Suh, Synthetic Metals 139,485 (2003); and B. Winther-Jensen, K. West, Macromol 0058 Norbornene and a ruthenium(IV)-based catalyst ecules 37, 4538 (2004), each of which is incorporated by Volatilized in a chamber under low pressure can result in a reference in its entirety.) film of polynorbonene on a silicon substrate. (H. W. Gu, D. 0061. A method of making a conducting material can be a Fu, L. T. Weng, J. Xie, and B. Xu, "Solvent-less polymeriza chemical vapor deposition (CVD) process that forms thin tion to grow thin films on solid substrates.” Advanced Func films of electrically active polymers. (See, for example, U.S. tional Materials 14(5), 492-500 (2004), which is incorporated Pat. No. 7,618,680 and references cited therein, each of which by reference in its entirety.) The monomer can undergo a is incorporated by reference in its entirety.) In one embodi ring-opening metathesis polymerization mechanism when ment, the technique can make PEDOT that has a conductivity contacted by the catalyst. (T. M. Trnka and R. H. Grubbs, over 4 S/cm and can be spectroscopically comparable to “The development of L2X2Ru=CHR olefin metathesis cata commercial product deposited from the Solution phase. This lysts: An organometallic Success story.” Accounts of Chemi technique can be applicable to other oxidatively polymerized cal Research 34(1), 18-29 (2001), which is incorporated by conducting materials like polypyrrole, polyaniline, poly reference in it entirety.) The technique can be repeated based thiophene, or their substituted derivatives. Side reactions on the same polymerization mechanism using 1.3.5.7-cy Stemming from acid generation during oxidative polymeriza clooctatetetraene to form polyacetylene. (H. W. Gu, R. K. tion can lead to bond breakage in the monomer and the for Zheng, X. X. Zhang, and B. Xu, "Using Soft lithography to mation of unconjugated oligomers that can result in films pattern highly oriented polyacetylene (HOPA) films via sol with low conductivities. These unwanted reactions can be vent-less polymerization.” Advanced Materials 16(15), 1356 minimized via three different methods: introducing pyridine (2004), which is incorporated by reference in its entirety.) The as a base, heating the Substrate (e.g., the Surface to be coated), deposition can be slow and an electrical conductivity was not and applying a bias to the sample stage. reported. 0062 CVD can be an all-dry process for depositing thin 0059 Electropolymerization of EDOT has been the most films of conducting polymers that are currently available on commonly used deposition technique for PEDOT and other the market only as Solution-based materials. Commercial conducting polymers. Electrode coatings and free-standing PEDOT films deposited onto anodes from solution can facili PEDOT films with conductivities around 300 S/cm can be tate hole injection and can result in significant efficiency created, which are an order of magnitude higher than the gains on the order of 50% for organic LED and photovoltaic conductivity of polypyrrole films deposited using the same devices. Using CVD to provide uniform coatings on rough method. Chemical oxidative polymerization of EDOT in a electrode surfaces can lead to further improvements in effi Solution containing oxidants like FeCls or Fe(OTs) can yield ciency by increasing the effective Surface area while avoiding PEDOT material with similar conductivities. The reaction sharp electrode features from protruding through the film and mixture can be cast on a surface leaving a polymerized film as shorting the device. The absence of the acidity associated the solvent evaporates and films may also be deposited on with solution-based films can reduce corrosion of neighbor Substrates that are immersed in the polymerizing reaction ing layers that can cause early device failure. Moderate stage mixture. However, like other conjugated polymers that adopt temperatures and vapor phase coating can allow depositing a very rigid conformation in order to maintain electron orbital conducting films on a wide range of unconventional organic overlap along the backbone, PEDOT can be insoluble and and inorganic high Surface-area materials, including paper, does not melt, precluding Subsequent processing. Bayer cir fabric, and small particles. CVD can be a significant tool for cumvented this problem by using a water soluble polyanion, organic semiconductor manufacturers seeking capabilities to polystyrene sulfonic acid (PSS), during polymerization as the incorporate conducting polymers in all-dry fabrication pro charge-balancing dopant. The aqueous PEDOT:PSS system, CCSSCS. now marketed as BAYTRON PTM, has a good shelf life and film forming capabilities while maintaining its transparency, Polymerization of EDOT. stability, and a conductivity of 10 S/cm. However, the PSS 0063. The oxidation of 3,4-ethylenedioxythiophene dopant can incorporate a non-conducting matrix material and (EDOT) to form PEDOT can be analogous to the oxidative US 2011/03 15204 A1 Dec. 29, 2011 polymerization of pyrrole, which has been described with a Chemical oxidant species can be extremely heavy, but can be mechanism proposed by Diaz. (S. Sadki, P. Schottland, N. Sublimed onto a Substrate Surface using a carrier gas and a Brodie, G. Sabouraud, Chemical Society Reviews 29, 283 heated, porous crucible installed inside the reactor directly (2000); and E. M. Genies, G. Bidan, A. F. Diaz, Journal of above the sample stage. The oxidant source can also be Electroanalytical Chemistry 149, 101 (1983), each of which installed on the exterior of the vacuum chamber. Evaporation is incorporated by reference in its entirety.) The first step can of the oxidant can also take place in a resistively heated be the oxidation of EDOT, which generates a radical cation container inside the reaction chamber. In certain embodi that has several resonance forms. The combination of two of ments, evaporation of the oxidant can take place in a resis these radicals and Subsequent deprotonation can form a neu tively heated container inside the reaction chamber. The oxi tral dimer. Substitution of the EDOT thiophene ring at the dant can be underneath the substrate surface to be coated. The 3,4-positions can block 3-coupling, allowing new bonds only monomer species can be provided to the Substrate surface, at the 2.5-positions. The alternating single and double bonds which may have been previously exposed to the oxidant. The of the dimer can give t-conjugated or delocalized electrons, monomer species can be provided to the reactor, for example, making it easier to remove an electron from the dimer relative in vapor form. In certain embodiments, the monomer species to the monomer. In other words, the dimer can have a lower can be delivered from a source external to the reactor. The oxidation potential than the monomer. The dimer can be oxidant can formathin, conformational layer on the Substrate oxidized to form another positively charged radical that can Surface. The conformational layer can react with monomer undergo coupling and deprotonation with other monomeric molecules as they adsorb. An acid-catalyzed side reaction can or oligomeric cations. Eventually, chains of neutral PEDOT lead to broken monomer bonds and non-conjugated oligo with alternating single and double bonds can be formed. mers can inhibit the formation of conjugated, electrically 0064. The neutral PEDOT polymer can be further oxi active polymer. These side reactions may be reduced using dized to create a positive charge along the backbone every one or more the following techniques: introducing a base, three or four chain segments. A "dopant' anion can ionically Such as pyridine, to react with any acid that is formed in situ; bind to the polymer and balance the charge. The oxidized heating the substrate to temperatures above about 60°C., 70° form of PEDOT can be a conducting form of the polymer. C., 80°C. or 90°C., for example, to accelerate evaporation of Neutral PEDOT can have a dark blue/purple color and the the acid as it is formed; and biasing the Substrate with a doped form can be very light blue. positive charge using a DC power Supply to favor the oxida 0065. The acidic strength of the reaction environment can tion of monomeric and oligomeric species adsorbed on the be one aspect of the mechanism to be considered, because it Substrate. Biasing can also provide directionality to charged can have a number of effects on the polymerization condi oligomers during polymer chain growth. The ordering of the tions, including the oxidation potential of the oxidant, which polymer chains that results can contribute to higher electrical can be decreased with the addition of a base. Some acidifica conductivities. tion of the reaction mixture can speed the rate of polymeriza 0069. The deposited film then can be heated, sometimes tion through an acid-initiated coupling mechanism, which under vacuum (e.g., -15 mmHg, -30 mmHg, or -45 mmHg). can contribute to additional chain growth. to remove unreacted monomer. Rinsing the dried film in a 0066. One caveat of acid-initiated coupling can be that the Solvent, for example, methanol or water, can remove reacted resulting polymer is not conjugated and may not be electri metal-containing oxidant from the film, in some cases can cally conducting without Subsequent oxidation. If the acidic change the color from hazy yellow to a clear sky blue hue. strength is too high, it can be possible to saturate the 3,4- Rinsing the dried film in a solution of "dopant” ionic salts, positions of a reacting EDOT radical, resulting in a trimer such as NOPF in acetonitrile, can promote the oxidized form with broken conjugation, quenching electrical conductivity. of the conducting polymer by balancing positive charges that (T. F. Otero, J. Rodriguez, Electrochimica Acta 39, 245 are induced along the polymer chain with anions from the (1994), which is incorporated by reference in its entirety). salt. 0067 Evidence has also been presented that very acidic conditions can break the dioxy bridge on the EDOT ring Methods of Making a Conducting Material. leading to imperfections that reduce conductivity. (B. Win 0070 A method of making a conducting material can ther-Jensen, K. West, Macromolecules 37, 4538 (2004), include providing a Substrate. The Substrate can have a Sur which is incorporated by reference in its entirety). Adding face area greater than area the Substrate occupies. The Sub pyridine as a base to the system to achieve an acidic strength strate can have a Surface area that is greater than 1.5 times, strong enough to maintain the oxidation potential of the oxi greater than 2 times, greater than 5 times, greater than 10 dant, but not strong enough to cause bond cleavage of the times, greater than 25 times, greater than 50 times, greater monomer, can yield PEDOT films with conductivities than 100 times, or greater than 500 times the area the substrate reported to be as high as 1000 S/cm. occupies. Oxidative Chemical Vapor Deposition (oCVD). (0071. In certain embodiments, the substrate can have a 0068 oOVD can generally take place in a reactor. Precur texture. For example, the texture can be fibrous, porous, Sor molecules, consisting of a chemical oxidant and a mono granulated, patterned, ridged, stippled, corrugated, perfo mer species, can be fed into the reactor. The oxidant can be a rated, milled, or brushed. The substrate can include more than metal-containing oxidant. This process can take place at a one texture, or a texture can be present on only a portion of the range of pressures from atmospheric pressure to low vacuum. substrate. The substrate can be flexible. In certain embodiments, the pressure can be about 760 Torr; 0072 The substrate can be a fibrous substrate, for in other embodiments, the pressure can be about 300 Torr; in example, paper or fabric. A fibrous Substrate can include other embodiments, the pressure can be about 30 Torr; in fibers, threads or filaments. Paper can be a felted sheet of other embodiments, the pressure can be about 3000 mTorr; in fibers deposited on a screen from a water Suspension. yet other embodiments, the pressure can be about 300 mTorr. Examples of paper can include rice paper, tracing paper, US 2011/03 15204 A1 Dec. 29, 2011

tissue paper, toilet paper, bathroom tissue, facial tissue, news gaseous. The oxidant can be vaporized to form a gaseous paper, wax paper, paper currency, banana paper, inkjet paper, oxidant. Vaporizing can include Sublimation using a carrier wallpaper, sandpaper, cotton paper, construction paper, book gas and a heated, porous crucible installed inside the reactor paper, printer paper, parchment, fish paper, TYVEKTM, wove directly above the sample stage where the substrate can be paper, buckypaper, and paper towels. Paper can be made from placed. Vaporization can also take place in a resistively heated a number of materials including plant fibers, for example, container inside the reaction chamber underneath the sub fibers from wood, cotton, rice, wheat, bark, bamboo, hemp, or strate surface. papyrus. Paper can also be made from materials including carbon, graphene oxide, or plastic. Products of any of these 0080. The oxidant can also be a metal-containing oxidant, materials, or combinations of any of these materials can also for example, iron(III) chloride, iron(III) tosylate, potassium be used to form paper. iodate, potassium chromate, ammonium Sulfate or tetrabuty 0073 Fabric can be a material made by weaving, felting or lammonium persulfate. The oxidant can have an oxidation knitting natural or synthetic fibers or filaments. A fabric can potential between about 0.5V and about 1.0 V, more specifi be made from natural Sources, which can include for example, cally, about 0.75 V. The entire surface can be contacted with from carbon, cotton, silk, fleece, fur, leather, angora, mohair, the oxidant or a portion of the Surface can be contacted. alpaca wool, Satin, goat wool, horse hair, flax, camel hair, Contacting the Substrate with the oxidant can form an oxi cashmere, vicuna fleece, llama wool, milk proteins, grass, dant-enriched portion of the substrate. The portion of the hemp, rush, straw, bamboo or wood. The fabrics made from Substrate can be a portion of the Surface. natural Sources can include linen, taffeta, tweed, wool, silk, I0081. The method of making a conducting material can canvas, cheesecloth, gauze, corduroy, denim, moleskin, pop include heating the oxidant enriched portion of the substrate. lin, sacking, terry cloth, lyocell, or Velvet. Minerals, such as Heating the oxidant enriched portion of the substrate can asbestos or basalt, can be used to make fabrics. Fabrics can be accelerate evaporation of acid that may be formed on the made from glass or metals, such as gold, silver, titanium, Substrate. The Substrate can be heated by heating a stage on aluminum, copper or steel. A fabric can be synthetic, for which the Substrate is placed, heating the reaction chamber or example, satin, rayon, acrylic, acetate, nylon, aramid, latex, other methods known to those of skill in art for heating a polyester, Spandex, chiffon, polyvinyl chloride, Sateen, ole substrate. fin, ingeo, lurex, tulle, or viscose. A fabric can be a blend of I0082 Acid-catalyzed side reactions during oCVD can natural materials, synthetic materials, or both. lead to broken monomer bonds and/or non-conjugated oligo 0074 The substrate can also be porous, meaning it can mers, which can inhibit the formation of conjugated, electri include pores or holes. A porous material can include, for cally active polymer. However, these side reactions may be example, plastic, sponge, ceramic, wood, clay, carbon or sili reduced using one or more the following techniques: intro CO. ducing a base. Such as pyridine, to react with any acid that is 0075. The substrate can be transparent or semi-transpar formed in situ; heating the Substrate to temperatures above ent. The substrate can allow greater than 90%, greater than about 60° C., 70° C., 80° C. or 90° C., for example, to 80%, greater than 70%, greater than 60%, greater than 50% or accelerate evaporation of the acid as it is formed; and biasing greater than 25% of light that contacts the substrate to pass the Substrate with a positive charge using a DC power Supply through the substrate. to favor the oxidation of monomeric and oligomeric species 0076. The light passing through the substrate can be light adsorbed on the substrate. Biasing also provided directional within the Solar spectrum. The light can include electromag ity to charged oligomers during polymer chain growth. The netic radiation with wavelengths falling in the visible spec ordering of the polymer chains that results may contribute to trum, the ultraviolet spectrum and the infrared spectrum. higher electrical conductivities. More specifically, the light can include electromagnetic I0083. The method of making a conducting material can radiation with a wavelength of 100 to 280 nm, 280 to 315 nm, include contacting the oxidant enriched surface with a base. 315 to 400 nm, 400 to 700 nm, 700 nm to 1 lum, 1 um to 2 um, The base can be a gaseous base. The base can be an optionally or 2 Lim to 3 um. The light can include electromagnetic radia substituted pyridine. tion classified as ultraviolet C, ultraviolet B, ultraviolet A, I0084. The method of making a conducting material can visible, infrared A, infrared B or infrared C. include contacting the oxidant enriched portion of the Sub 0077. The substrate can be free from pre-treatments. The strate with a monomer. The monomer may be gaseous. The Substrate can also be free from Solvents or wetting agents. The monomer can be vaporized to form a gaseous monomer. substrate can be hydrophobic or hydrophilic. Vaporizing can include Sublimation. The monomer can be 0078. The substrate can be fragile, for example, it can be vaporized inside the reaction chamber or gaseous monomer easily folded, shaped, torn or cut. The substrate can also be can be provided from a source external to the reaction cham easily damaged by common processing agents such as Sol ber. The monomer can be an optionally substituted thiophene, vents, plasmas or heat. The Substrate can be flexible, e.g., optionally substituted pyrrole, optionally substituted easily bent, folded or creased. A flexible substrate can be anilines, phenanthrolines, furans, heteroarenes including brittle or non-brittle. The substrate can be stretchable. more than one ring heteroatom, benzenoid arenes, non-ben 007.9 The method of making a conducting material can Zenoid aromatic compounds, or combinations thereof. The include coating at least a portion of a Surface of the Substrate monomer can be 3.4 ethylenedioxythiophene. Contacting the with a conductive polymer. Coating at least a portion of the oxidant-enriched surface with the monomer can result in Substrate with a conductive polymer can include oxidative polymerization of the monomer and the formation of a poly chemical vapor deposition, which can take place in a reactor mer coated Surface. or a reaction chamber. Coating at least a portion of a Surface I0085. In certain embodiments, the deposited film then of the Substrate with a conductive polymer can include con may be heated, sometimes under vacuum (e.g., 15 mmHg, 30 tacting the Substrate with an oxidant. The oxidant can be mmHg, or 45 mmHg), to remove unreacted monomer. US 2011/03 15204 A1 Dec. 29, 2011

I0086 Following polymerization, the polymer coated sur a high degree of adhesion to the Substrate. The high degree of face can be washed with a solvent, which can be, for example, adhesion can result from in situ covalent bonding, or chemical water, methanol, ethanol, isopropanol, acetonitrile or mix grafting, of the polymer to a Substrate possessing functional tures thereof. In some cases, this changes the color from hazy groups upon film formation. Functional groups can be present yellow to a clear sky blue hue. on polystyrenes or polyethylene terephthalates, for example. 0087. A gaseous precursor, such as an epoxide, can be The high degree of adhesion can be advantageous for roll-to thermally activated to provide an initiator for the oxidative roll processing and for flexible and stretchable electronics, polymerization of the conductive polymer. The precursor can where mechanical stresses could otherwise result in cracking be thermally activated with the use of a hot filament. The or delamination. polymer coating can include bicyclic thiophene, for example, 0092. The conductive polymer coating can be of a uniform a heterobicyclic thiophene such as poly(3,4-ethylenediox thickness (i.e., said thickness does not vary more than 10% ythiophene). over the surface of the article; or by more than 5% over the 0088. The method of making a conducting material can surface of the article; or by more than 1% over the surface of include contacting the conductive polymer coated Substrate the article). The thickness of the polymer coating can be with a dopant, most commonly a dopant anion. A dopant can between 0 and 100 nm, for example, between 0 and 10 nm, contribute to the conductivity of the polymer coating. A between 10 and 20 nm, between 20 and 30 nm, between 30 dopant anion can provide stability enhancement for electro and 40 nm, between 40 and 50 nm, between 50 and 75 nm, active polymers. The dopant may be any compound as long as between 75 and 100 nm. The thickness of the polymer coating it has a doping ability (i.e. stabilizing ability). For example, an can be greater than 100 nm. More specifically, the thickness organic sulfonic acid, an inorganic Sulfonic acid, an organic of the polymer coating can be 5 nm, 10 nm, 15 nm, 20 nm, 25 carboxylic acid or salts thereof such as a metal salt or an nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 75 nm, 80 nm, 90 nm. ammonium salt may be used. More specifically, it can include or 100 nm. chloride, bromide, iodide, fluoride, phosphate, sulfonate or 0093. The conductive polymer coating can have a mass nitrosonium hexafluorophosphate. The dopant can be added per surface area of less than about 500 ug/cm, less than about to the oxidizing agent and/or the monomer, can be allowed to 100 g/cm, less than about 50 g/cm, less than about 10 be present together at the time of polymerization or can be ug/cm, or less than about 5ug/cm. The required mass per added by other methods known to those of skill in the art. In Surface area depends on the specific Surface area of the Sub certain embodiments the dopant molecule comprises aqueous strate to be coated. A smooth flat substrate, 1 cm in area can solutions of the acids selected from the group consisting of require coverage of only 1 cm of area and thus the specific phosphoric acid, triflic acid, hydrochloric acid, methane surface area of 1 cm/cm. However, a 1 cm section of fabric Sulfonic acid, oxalic acid, pyruvic acid, or acrylic acid, or a can have a specific Surface area greater than 1 because each polyanion incorporating one or more of the aforementioned surface-accessible fiber of the fabric must be coated. The types of acids. In certain embodiments, rinsing the dried film gaseous reactants of the inventive processes can penetrate in a solution of "dopant” ionic salts, such as NOPF in aceto into the fabric and coat these internal surfaces. The specific nitrile, can promote the oxidized form of a conducting poly Surface area can depend on the packing density of the fibers merby balancing positive charges that are induced along the and total thickness of the fabric. The thickness (cm) of the polymer chain with anions from the salt. coating multiplied by the specific surface area (cm/cm) of 0089. Once the conductive polymer is formed, the conduc the fabric and the density of the coating (g/cm) will yield the tive polymer coated Surface can be heated under vacuum to mass per surface area (g/cm). dry. The Surface can be heated using a heated Stage, heating 0094. The methods of making a conducting material can the reaction chamber, or heated by other methods known to have several advantages. In addition to achieving polymer those of skill in the art. ization from vapor-phase reactants and conformal thin-film 0090 Substrates can have textured surfaces that require formation in a single step, the method can impart excellent fabrication processes capable of conformally coating com Substrate adhesion through in situ covalent bonding (chemi plex geometries. The conductive polymer can be conformal to cal grafting) and can allow direct control over thickness, the Substrate. For example, the polymer can form a layer dopant concentration, work function, and conductivity. (Im. directly around the fibers of the substrate (FIG. 7?), can form S. G., Yoo, P. J., Hammond, P. T., Gleason, K. K., Grafted a layer directly in holes of a porous or perforated substrate conducting polymer films for nano-patterning onto various (not shown), or can form a layer directly over granulated, organic and inorganic Substrates by oxidative chemical vapor ridged, patterned, stippled, corrugated, milled, or brushed deposition. Adv. Mater. 19, 2863 (2007): Im, S.G., Gleason, substrates (not shown). This allows the conductive polymer to K. K. Systematic control of the electrical conductivity of get into the “nooks and crannies of the substrate. The con poly(3,4-ethylenedioxythiophene) via oxidative chemical ductive polymer coating can have essentially the same shape vapor deposition. Macromolecules 40, 6552 (2007); and Im. and contours of the Substrate, for example, forming a sleeve S.G., Gleason, K. K., Olivetti, E. A., Doping level and work on the fibers. This is in contrast to conductive polymers function control in oxidative chemical vapor deposited poly deposited on substrates by techniques other than oCVD, (3.4-ethylenedioxythiophene). Appl. Phys. Lett. 90 (2007), where the conductive polymer can blanket the substrate (FIG. each of which is incorporated by reference in its entirety). 7e) or can have irregular dimensions along the texture of the Films can form at low substrate temperatures (20-100° C.), substrate and demonstrate poor morphology (FIG. 7d). moderate vacuum (-0.1 Torr), and at rates that can exceed 10 0091. The conductive polymer can directly conform to the nm min'. Moreover, since there are no solubility require substrate. Pre-treatment steps or protective layers may not be ments, the polymer coated Substrates may not be bound by the required for the conductive polymer to adhere to the substrate. molecular weight and dopant restrictions that can limit con Pre-treatment steps can include exposing the Substrate to ductivity in solution-cast polymers. (Ha, Y. H. et al., Towards Solvents or wetting agents. The conductive polymer can have a transparent, highly conductive poly(3,4-ethylenediox US 2011/03 15204 A1 Dec. 29, 2011

ythiophene). Adv. Funct. Mater. 14, 615 (2004), which is made from glass or metals, such as gold, silver, titanium, incorporated by reference in its entirety). Finally, the method aluminum, copper or steel. A fabric can be synthetic, for can be achieved by all dry processing. example, satin, rayon, acrylic, acetate, nylon, aramid, latex, 0095 Conducting polymers can be fabricated directly on polyester, Spandex, chiffon, polyvinyl chloride, Sateen, ole ultra-lightweight “everyday Substrates, including as-pur fin, ingeo, lurex, tulle, or viscose. A fabric can be a blend of chased fiber-based papers (-0.001 g cm, ~40-um thick), natural materials, synthetic materials, or both. without any pretreatment steps or protecting layers. Photo 0101 The substrate can also be porous, meaning it can Voltaics formed using this technique can demonstrate power include pores or holes. A porous material can include, for to-weight ratios over 500 W kg. The highly conductive example, plastic, sponge, ceramic, wood, clay, carbon or sili polymer electrodes (100-1000S cm) can be simultaneously CO. synthesized and deposited without solvents as conformal, 0102 The substrate can be transparent or semi-transpar transparent thin films at low temperature via oxidative chemi ent. The substrate can allow greater than 90%, greater than cal vapor deposition (oCVD). The polymer electrodes can 80%, greater than 70%, greater than 60%, greater than 50% or retain their electrical integrity even after severe deformation: greater than 25% of light that contacts the substrate to pass >1000 flexing cycles at <5 mm radius, >100 creasing cycles, through the substrate. and stretching to ~200%. The polymer electrodes can exhibit 0103) The light passing through the substrate can be light comparable performance to conventional ITO-based devices, within the Solar spectrum. The light can include electromag can be flexed >100 times while maintaining nearly 100% of netic radiation with wavelengths falling in the visible spec their starting efficiencies, and can retain power generation in trum, the ultraviolet spectrum and the infrared spectrum. air when folded into large-area three-dimensional structures. More specifically, the light can include electromagnetic radiation with a wavelength of 100 to 280 nm, 280 to 315 nm, Conducting Material. 315 to 400 nm, 400 to 700 nm, 700 nm to 1 lum, 1 um to 2 um, 0096. A conducting material can include a substrate and a or 2 Lim to 3 um. The light can include electromagnetic radia conductive polymer coating on a surface of the Substrate tion classified as ultraviolet C, ultraviolet B, ultraviolet A, (FIG. 9a). visible, infrared A, infrared B or infrared C. 0097. The substrate can have a surface area greater than 0104. The substrate can be free from pre-treatments. The area the Substrate occupies. The Substrate can have a Surface Substrate can also be free from Solvents or wetting agents. The area that is greater than 1.5 times, greater than 2 times, greater substrate can be hydrophobic or hydrophilic. than 5 times, greater than 10 times, greater than 25 times, 01.05 The substrate can be fragile, for example, it can be greater than 50 times, greater than 100 times, or greater than easily folded, shaped, torn, or cut. The Substrate can also be 500 times the area the substrate occupies. easily damaged by common processing agents such as Sol 0098. The substrate can have a texture. For example, the vents, plasmas or heat. The Substrate can be flexible, e.g., texture can be fibrous, porous, granulated, patterned, ridged, easily bent, folded or creased. A flexible substrate can be stippled, corrugated, perforated, milled or brushed. The sub brittle or non-brittle. The substrate can be stretchable. strate can include more than one texture, or a texture can be 0106 The conductive polymer can include monomeric present on only a portion of the substrate. The substrate can be units derived from optionally substituted thiophenes, option flexible. ally Substituted pyrroles, optionally Substituted anilines, 0099. The substrate can be a fibrous substrate, for phenanthrolines, furans, heteroarenes including more than example, paper or fabric. A fibrous Substrate can include one ring heteroatom, benzenoid arenes, non-benzenoid aro fibers, threads or filaments. Paper can be a felted sheet of matic compounds, or combinations thereof. The polymer fibers deposited on a screen from a water Suspension. coating can include bicyclic thiophene, for example, a het Examples of paper can include rice paper, tracing paper, erobicyclic thiophene such as poly(3,4-ethylenediox tissue paper, toilet paper, bathroom tissue, facial tissue, news ythiophene). Poly(3,4-ethylenedioxythiophene) can be made paper, wax paper, paper currency, banana paper, inkjet paper, up of monomeric units derived from 3.4 ethylenediox wallpaper, sandpaper, cotton paper, construction paper, book ythiophene. paper, printer paper, parchment, fish paper, TYVEKTM, wove 0107 The conductive polymer can be a p-type semicon paper, buckypaper, or paper towels. Paper can be made from ductor and have an excess of holes (i.e. spaces that accept a number of materials including plant fibers, for example, electrons). The conductive polymer can be an n-type semi fibers from wood, cotton, rice, wheat, bark, bamboo, hemp, or conductor and have an excess of free electrons. papyrus. Paper can also be made from materials including 0.108 Substrates can have textured surfaces that require carbon, graphene oxide, or plastic. Products of any of these fabrication processes capable of conformally coating com materials, or combinations of any of these materials can also plex geometries. The conductive polymer can be conformal to be used to form paper. the Substrate. For example, the polymer can form a layer 0100 Fabric can be a material made by weaving, felting or directly around the fibers of the substrate (FIG. 7?), can form knitting natural or synthetic fibers or filaments. A fabric can a layer directly in holes of a porous or perforated substrate be made from natural Sources, which can include for example, (not shown), or can form a layer directly over granulated, from carbon, cotton, silk, fleece, fur, leather, angora, mohair, ridged, patterned, stippled, corrugated, milled, or brushed alpaca wool, Satin, goat wool, horse hair, flax, camel hair, substrates (not shown). This allows the conductive polymer to cashmere, vicuna fleece, llama wool, milk proteins, grass, get into the “nooks and crannies of the substrate. The con hemp, rush, straw, bamboo or wood. The fabrics made from ductive polymer coating can have essentially the same shape natural Sources can include linen, taffeta, tweed, wool, silk, and contours of the Substrate, for example, forming a sleeve canvas, cheesecloth, gauze, corduroy, denim, moleskin, pop on the fibers. This is in contrast to conductive polymers lin, sacking, terry cloth, lyocell, or Velvet. Minerals, such as deposited on substrates by techniques other than oCVD, asbestos or basalt, can be used to make fabrics. Fabrics can be where the conductive polymer can blanket the substrate (FIG. US 2011/03 15204 A1 Dec. 29, 2011

7e) or can have irregular dimensions along the texture of the cycles, or stretching greater than 150%. Withstanding the substrate and demonstrate poor morphology (FIG. 7d). deformation can be determined by observing the presence or 0109 The conductive polymer can directly conform to the absence of physical damage to the conducting material, for substrate. Pre-treatment steps or protective layers may not be example, cracks, tears, ruptures, Snags, pills, unravels, pleats, required for the conductive polymer to adhere to the substrate. creases, or changes in color, shape or thickness. Withstanding Pre-treatment steps can include exposing the Substrate to the deformation can be determined by measuring properties Solvents or wetting agents. The conductive polymer can have of the conducting material Such as current density-Voltage a high degree of adhesion to the Substrate. The high degree of characteristics, work function, tensility or temperature. adhesion can result from in situ covalent bonding, or chemical 0114. A method of testing the conducting material can grafting, of the polymer to a Substrate possessing functional include making the conducting material and comparing it to a groups upon film formation. The high degree of adhesion can control device. The control device can have the structure be advantageous for roll-to-roll processing and for flexible ITO/PEDOT:PSS/CuPc/C/BCP/Ag. In particular, it can and stretchable electronics, where mechanical stresses could have the structure ITO (100 nm)/PEDOT:PSS (70 nm)/CuPc otherwise result in cracking or delamination. (20 nm)/Co (40 nm)/BCP (12 nm)/Ag (1000 nm). A control 0110. The conductive polymer coating can be of a uniform electrode can be the ITO/oCVD PEDOT electrode. A method thickness (i.e., said thickness does not vary more than 10% of testing the conducting material can also include measuring over the surface of the article; or by more than 5% over the the current density-Voltage characteristics. surface of the article; or by more than 1% over the surface of 0115 The conducting material can perform comparably the article). The thickness of the polymer coating can be with conventional anode structures and exhibit improved between 0 and 10 nm, between 10 and 20 nm, between 20 and open-circuit voltage relative to bare ITO. The conducting 30 nm, between 30 and 40 nm, between 40 and 50 nm, material can provide advantageous work function and mor between 50 and 75 nm, between 75 and 100 nm or greater than phological benefits. The conducting material can be more 100 nm. More specifically, the thickness of the polymer coat conductive than a control electrode, for example, order of ing can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, magnitude or more conductive than a PEDOT:PSS buffer 50 nm, 60 nm, 70 nm, 75 nm, 80 nm, 90 nm or 100 nm. layer. A higher fill factor can be exhibited by the conducting 0111. The conductive polymer coating can have a mass material when compared to the control electrode. per surface area of less than about 500 g/cm, less than about 100 g/cm, less than about 50 g/cm, less than about 10 Light Absorbing or Light Emitting Device. ug/cm, or less than about 5ug/cm. The required mass per 0116. A light absorbing or a light emitting device can Surface area depends on the specific Surface area of the Sub include a Substrate and a conductive polymer coating on a strate to be coated. A smooth flat substrate, 1 cm in area can surface of the substrate. The substrate with a conductive poly require coverage of only 1 cm of area and thus the specific mer coating on a surface of the Substrate can be a conducting surface area of 1 cm/cm. However, a 1 cm section of fabric material. The conducting material can be part of a light can have a specific Surface area greater than 1 because each absorbing device, for example, a photovoltaic. The conduct surface-accessible fiber of the fabric must be coated. The ing material can be part of a light emitting device, for gaseous reactants of the inventive processes can penetrate example, a light emitting diode. into the fabric and coat these internal surfaces. The specific 0117 The substrate can have a surface area greater than Surface area can depend on the packing density of the fibers area the Substrate occupies. The Substrate can have a Surface and total thickness of the fabric. The thickness (cm) of the area that is greater than 1.5 times, greater than 2 times, greater coating multiplied by the specific surface area (cm/cm) of than 5 times, greater than 10 times, greater than 25 times, the fabric and the density of the coating (g/cm) will yield the greater than 50 times, greater than 100 times, or greater than mass per surface area (g/cm). 500 times the area the substrate occupies. 0112 The conductive polymer coating can also include a 0118. The substrate can have a texture. For example, the dopant, most commonly a dopant anion. A dopant can con texture can be fibrous, porous, granulated, patterned, ridged, tribute to the conductivity of the polymer coating. A dopant stippled, corrugated, perforated, milled or brushed. The sub anion can provide stability enhancement for electroactive strate can include more than one texture, or a texture can be polymers. The dopant may be any compound as long as it has present on only a portion of the substrate. The substrate can be a doping ability (i.e. charge stabilizing ability). For example, flexible. an organic Sulfonic acid, an inorganic Sulfonic acid, an 0119 The substrate can be a fibrous substrate, for organic carboxylic acid or salts thereof such as a metal salt or example, paper or fabric. A fibrous Substrate can include an ammonium salt may be used. More specifically, it can fibers, threads or filaments. Paper can be a felted sheet of include chloride, bromide, iodide, fluoride, phosphate, sul fibers deposited on a screen from a water Suspension. fonate or nitrosonium hexafluorophosphate. In certain Examples of paper can include rice paper, tracing paper, embodiments the dopant molecule comprises aqueous solu tissue paper, toilet paper, bathroom tissue, facial tissue, news tions of the acids selected from the group consisting of phos paper, wax paper, paper currency, banana paper, inkjet paper, phoric acid, triflic acid, hydrochloric acid, methanesulfonic wallpaper, sandpaper, cotton paper, construction paper, book acid, oxalic acid, pyruvic acid, and acrylic acid, or a poly paper, printer paper, parchment, fish paper, TYVEKTM, wove anion incorporating one or more of the aforementioned types paper, buckypaper, or paper towels. Paper can be made from of acids. a number of materials including plant fibers, for example, 0113. The conducting material can withstand deformation fibers from wood, cotton, rice, wheat, bark, bamboo, hemp, or including repeated folding, stretching, bending, arching, roll papyrus. Paper can also be made from materials including ing, or perforations. The conducting material can withstand carbon, graphene oxide, or plastic. Products of any of these severe deformation, including greater than 1000 flexing materials, or combinations of any of these materials can also cycles (less than 5 mm radius), greater than 100 creasing be used to form paper. US 2011/03 15204 A1 Dec. 29, 2011

0120 Fabric can be a material made by weaving, felting or easily damaged by common processing agents such as Sol knitting natural or synthetic fibers or filaments. A fabric can vents, plasmas or heat. The Substrate can be flexible, e.g., be made from natural Sources, which can include for example, easily bent, folded or creased. A flexible substrate can be from carbon, cotton, silk, fleece, fur, leather, angora, mohair, brittle or non-brittle. The substrate can be stretchable. alpaca wool, Satin, goat wool, horse hair, flax, camel hair, I0128. The conductive polymer can include monomeric cashmere, vicuna fleece, llama wool, milk proteins, grass, units derived from optionally substituted thiophenes, option hemp, rush, straw, bamboo or wood. The fabrics made from ally Substituted pyrroles, optionally Substituted anilines, natural Sources can include linen, taffeta, tweed, wool, silk, phenanthrolines, furans, heteroarenes including more than canvas, cheesecloth, gauze, corduroy, denim, moleskin, pop one ring heteroatom, benzenoid arenes, non-benzenoid aro lin, sacking, terry cloth, lyocell, or Velvet. Minerals, such as matic compounds, or combinations thereof. The polymer asbestos or basalt, can be used to make fabrics. Fabrics can be coating can include bicyclic thiophene, for example, a het made from glass or metals, such as gold, silver, titanium, erobicyclic thiophene such as poly(3,4-ethylenediox aluminum, copper or steel. A fabric can be synthetic, for ythiophene). Poly(3,4-ethylenedioxythiophene can be made example, satin, rayon, acrylic, acetate, nylon, aramid, latex, up of monomeric units derived from 3.4 ethylenediox polyester, Spandex, chiffon, polyvinyl chloride, Sateen, ole ythiophene. fin, ingeo, lurex, tulle, or viscose. A fabric can be a blend of I0129. The conductive polymer can be a p-type semicon natural materials, synthetic materials, or both. ductor and have an excess of holes (i.e. spaces that accept 0121 The Substrate can also be porous, meaning it can electrons). The conductive polymer can be an n-type semi include pores or holes. A porous material can include, for conductor and have an excess of free electrons. example, plastic, sponge, ceramic, wood, clay, carbon or sili 0.130. Substrates can have textured surfaces that require CO. fabrication processes capable of conformally coating com 0122. In certain embodiments, the substrate can be a plas plex geometries. The conductive polymer can be conformal to tic, for example, polystyrene, polyamide, polyvinyl chloride, the Substrate. For example, the polymer can form a layer polyethylene, acrylonitrile butadiene styrene, polyester, directly around the fibers of the substrate (FIG. 7?), can form polyurethane, polypropylene, polycarbonate, polyvinylidene a layer directly in holes of a porous or perforated substrate chloride, polymethyl methacrylate, polytetrafluoroethylene, (not shown), or can form a layer directly over granulated, polyetheretherketone, polyetherimide, phenolic, urea-form ridged, patterned, stippled, corrugated, milled, or brushed aldehyde, melamine formaldehyde, polylactic acid, plas substrates (not shown). This allows the conductive polymer to tarch, polyethylene terephthalate or combination thereof. The get into the “nooks and crannies of the substrate. The con Substrate can also be an elastomer Such as polydimethylsilox ductive polymer coating can have essentially the same shape ane, latex or rubber. The plastic can be solid or textured. and contours of the Substrate, for example, forming a sleeve 0123. A surface of the substrate can include a plurality of on the fibers. This is in contrast to conductive polymers functional groups. A functional group can include a hydrox deposited on substrates by techniques other than oCVD, ide, an alkane, an aliphatic ring, an alkene, a benzenoid ring, where the conductive polymer can blanket the substrate (FIG. a thiol, an oxime, a thiocyanate, a cyanamide, a Sulfonic acid, 7e) or can have irregular dimensions along the texture of the a phosphinic acid, a thiophosphate acid, an aldehyde, a substrate and demonstrate poor morphology (FIG. 7d). ketone, an alkyne, a carboxylic acid, a carbonyl, an ester, an I0131 The conductive polymer can directly conform to the ether, an amide, an amine, a halide, a phenol or a nitrile. Substrate. Pre-treatment steps or protective layers may not Functional groups can include an aromatic functional group required for the conductive polymer to adhere to the substrate. Such as an aromatic ester, an aromatic amide, an aromatic Pre-treatment steps can include exposing the Substrate to nitro, a phenol, a benzenoid, a benzene, an aromatic ester or Solvents or wetting agents. The conductive polymer can have an aromatic carboxylic acid. The polymer can interact, e.g. a high degree of adhesion to the Substrate. The high degree of bond, with the functional groups on the Substrate. A bond can adhesion can result from in situ covalent bonding, or chemical be a covalent, ionic, Vander Waals, dipolar or hydrogen bond. grafting, of the polymer to a Substrate possessing functional 0.124. The substrate can be transparent or semi-transpar groups upon film formation. The high degree of adhesion can ent. The substrate can allow greater than 90%, greater than be advantageous for roll-to-roll processing and for flexible 80%, greater than 70%, greater than 60%, greater than 50% or and stretchable electronics, where mechanical stresses could greater than 25% of light that contacts the substrate to pass otherwise result in cracking or delamination. through the substrate. 0.132. The conductive polymer coating can be of a uniform 0.125. The light passing through the substrate can be light thickness (i.e., said thickness does not vary more than 10% within the Solar spectrum. The light can include electromag over the surface of the article; or by more than 5% over the netic radiation with wavelengths falling in the visible spec surface of the article; or by more than 1% over the surface of trum, the ultraviolet spectrum or the infrared spectrum. More the article). The thickness of the polymer coating can be specifically, the light can include electromagnetic radiation between 0 and 10 nm, between 10 and 20 nm, between 20 and with a wavelength of 100 to 280 nm, 280 to 315 nm, 315 to 30 nm, between 30 and 40 nm, between 40 and 50 nm, 400 nm, 400 to 700 nm, 700 nm to 1 um, 1 um to 2 um, or 2 between 50 and 75 nm, between 75 and 100 nm or greater than um to 3 um. The light can include electromagnetic radiation 100 nm. More specifically, the thickness of the polymer coat classified as ultraviolet C, ultraviolet B, ultraviolet A, visible, ing can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, infrared A, infrared B or infrared C. 50 nm, 60 nm, 70 nm, 75 nm, 80 nm, 90 nm or 100 nm. 0126 The substrate can be free from pre-treatments. The I0133. The conductive polymer coating can have a mass Substrate can also be free from Solvents or wetting agents. The per surface area of less than about 500ug/cm, less than about substrate can be hydrophobic or hydrophilic. 100 g/cm, less than about 50 g/cm, less than about 10 0127. The substrate can be fragile, for example, it can be ug/cm, or less than about 5ug/cm. The required mass per easily folded, shaped, torn, or cut. The Substrate can also be Surface area depends on the specific Surface area of the Sub US 2011/03 15204 A1 Dec. 29, 2011

strate to be coated. A smooth flat substrate, 1 cm in area can electrode can include indium tin oxide, gallium indium tin require coverage of only 1 cm of area and thus the specific oxide, Zinc indium tin oxide, titanium nitride or polyaniline. surface area of 1 cm/cm. However, a 1 cm section of fabric 0140. The cathode can be patterned. The anode (i.e. the can have a specific Surface area greater than 1 because each polymer or the second electrode) can also be patterned. The surface-accessible fiber of the fabric must be coated. The electrodes of the device can be connected to a Voltage source gaseous reactants of the inventive processes can penetrate by electrically conductive pathways. into the fabric and coat these internal surfaces. The specific 0.141. The energy converting region can convert energy Surface area can depend on the packing density of the fibers between photoenergy and electric energy. In particular, the and total thickness of the fabric. The thickness (cm) of the energy converting region can convert photoenergy into elec coating multiplied by the specific surface area (cm/cm) of tric energy. For a light absorbing device, light can strike the the fabric and the density of the coating (g/cm) will yield the light absorbing device on the surface of the substrate. The mass per surface area (g/cm). Substrate can be transparent or semi-transparent, allowing 0134. The conductive polymer coating can also include a light to pass through to the energy converting region. AS light dopant, most commonly a dopant anion. A dopant can con interacts with the energy converting region, photons can be tribute to the conductivity of the polymer coating. A dopant absorbed by the molecules, causing them to expel electrons anion can provide stability enhancement for electroactive and establishing a current. The energy converting region can polymers. The dopant may be any compound as long as it has include a light absorber, Such as, for example, copper phtha a doping ability (i.e. charge stabilizing ability). For example, locyanine, fullerene-Co or bathocuprine. The energy con an organic Sulfonic acid, an inorganic Sulfonic acid, an Verting region can also include silicon, copper indium dis organic carboxylic acid or salts thereof such as a metal salt or elenide, Zinc oxide, Zinc sulfide, Zinc selenide, Zinc telluride, an ammonium salt may be used. More specifically, it can cadmium oxide, cadmium sulfide, cadmium selenide, cad include chloride, bromide, iodide, fluoride, phosphate, sul mium telluride, magnesium oxide, magnesium sulfide, mag fonate or nitrosonium hexafluorophosphate. In certain nesium selenide, magnesium telluride, mercuric oxide, mer embodiments the dopant molecule comprises aqueous solu curic sulfide, mercuric selenide, mercuric telluride, tions of the acids selected from the group consisting of phos aluminum nitride, aluminum phosphide, aluminum arsenide, phoric acid, triflic acid, hydrochloric acid, methanesulfonic aluminum antimonide, gallium nitride, gallium phosphide, acid, oxalic acid, pyruvic acid, and acrylic acid, or a poly gallium arsenide, gallium antimonide, indium nitride, indium anion incorporating one or more of the aforementioned types phosphide, indium arsenide, indium antimonide, thallium of acids. nitride, thallium phosphide, thallium arsenide, thallium anti 0135 The conducting material can withstand deforma monide, lead sulfide, lead selenide, lead telluride or combi tion, including repeated, folding, stretching, bending, arch nations thereof. Specifically, the energy converting region can ing, rolling, or perforations. The conducting material can be a CuPc/C/BCP/Ag molecular organic heterojunction. withstand severe deformation, including greater than 1000 0142. The energy converting region can include two or flexing cycles (less than 5 mm radius), greater than 100 creas more layers of materials. The layers can be deposited on a ing cycles, and stretching greater than 150%. Withstanding surface of one of the electrodes by oxidative chemical vapor the deformation can be determined by observing the presence deposition, spin coating, dip coating, vapor deposition, sput or absence of physical damage to the conducting material, for tering, or other thin film deposition methods. The layers can example, cracks, tears, ruptures, Snags, pills, unravels, pleats, include a p-type semiconductorandan n-type semiconductor. creases, or changes in color, shape or thickness. Withstanding The layers can include a hole-injecting layer, a photoactive the deformation can be determined by measuring properties layer and/or an electron donating layer. of the conducting material Such as current density-Voltage 0.143 A material can be a photoactive material and include characteristics, work function, tensility, or temperature. at least one dye. The photoactive material can include a plu 0136. A light absorbing or light emitting device can rality of dyes. Examples of dyes can include black dyes (e.g., include an electrode and an energy converting region (FIG. tris(isothiocyanato)-ruthenium (II)-2,2': 6'2"-terpyridine-4, 9b). The energy converting region can be between the con 4',4'-tricarboxylic acid, tris-tetrabutylammonium salt), ductive polymer and the electrode. orange dyes (e.g., tris(2,2'-bipyridyl-4,4'-dicarboxylato) 0.137 The electrode can include Al, Au, Ag, Ba, Yb, Ca, a ruthenium (II) dichloride, purple dyes (e.g., cis-bis(isothio lithium-aluminum alloy, a magnesium-silver alloy, indium cyanato)bis-(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium tin oxide, gallium indium tin oxide, Zinc indium tin oxide, (II)), red dyes (e.g., an eosin), green dyes (e.g., a merocya titanium nitride or polyaniline. The electrode can be sand nine) or blue dyes (e.g., a cyanine). Examples of additional wiched, sputtered, or evaporated onto the energy converting dyes include cyanines, Xanthenes, anthraquinones, merocya region. nines, phenoxazinones, indolines, thiophenes, coumarins, 0138. In some embodiments, a second electrode can be anthocyanins, porphyrins, phthalocyanines, squarates, present in addition to the first electrode and the conductive squarylium dyes, or certain metal-containing dyes. Combi polymer (FIG. 9c). In this case, the second electrode can be nations of dyes can also be used within a given region so that located on the substrate. However, in some embodiments, the a given region can include more than one (e.g., two, three, conductive polymer can replace a second electrode. In these four, five, six, seven) different dyes. The dye(s) can be sorbed circumstances, the electrode can be a cathode and the con (e.g., chemisorbed and/or physisorbed) on the nanoparticles. ductive polymer can be an anode. A dye can be selected, for example, based on its ability to 0.139. As previously stated, a second electrode can also be absorb photons in a wavelength range of operation (e.g., present. One possible configuration when the second elec within the visible spectrum), its ability to produce free elec trode is present can be for the first electrode to be a cathode, trons (or electron holes) in a conduction band of the nanopar the second electrode to be an anode and the conductive poly ticles, its effectiveness in complexing with or Sorbing to the mer to be part of the energy converting region. The second nanoparticles, and/or its color. US 2011/03 15204 A1 Dec. 29, 2011

0144. The layers can be optimized to absorb energy from transfer of energy without light emission and reabsorption photons within the spectrum of solar light. In other words, (such as Förster energy transfer). In either case, once the photons from the Solar spectrum have energy within the band emission-altering material is in an excited State, it can emit gap of the materials comprising the layers of the energy light. In some circumstances, emission and reabsorption can converting region. Different layers of the energy converting be the primary method of energy transfer. When this is so, the region may have band gaps corresponding to different por emission-altering material need not be adjacent to the emis tions of the Solar spectrum. The Solar spectrum can include sive material. The efficiency of Förster energy transfer, how electromagnetic radiation having a wavelength within the ever, depends on the distance between the energy transfer ultraviolet A region, ultraViolet B region, ultraviolet C region, partners, with Smaller distances giving greater efficiency of visible light region, infrared A region, infrared B region or energy transfer. infrared C region. 0151. Devices can be prepared that emit visible or infrared 0145 Individual light absorbing devices can be formed at light. Properties of semiconductor materials in the energy multiple locations on a single Substrate to formalight absorb converting region can be selected Such that the nanocrystal ing system. The system can include devices that absorb pho emits visible or infrared light of a selected wavelength. The tons from light of different wavelengths. The system can also wavelength can be between 300 and 2,500 nm or greater, for include different substrates or conductive polymer. instance between 300 and 400 nm, between 400 and 700 nm, 0146 Light absorbing devices can be incorporated into a between 700 and 1100 nm, between 1100 and 2500 nm, or number of apparatuses including, for example, curtains, greater than 2500 nm. shingles, architectural elements, artistic pieces, clothes, tents, 0152 Individual light emitting devices can be formed at portable power Supplies, shelters, shoes, wallpaper, portable multiple locations on a single Substrate to form a display. The electronic devices (i.e. phones, calculators, radios, mp3 play display can include devices that emit at different wave ers) or newspapers. lengths. By patterning the substrate with arrays of different 0147 For a light emitting device, the energy converting color-emitting semiconductor nanocrystals, a display includ region can convert electric energy into photoenergy. A volt ing pixels of different colors can be formed. age can be applied between the two electrode on either side of 0153. The device can be made in a controlled (oxygen-free the energy converting region. This can Supply current, which and moisture-free) environment, preventing the quenching of can increase the energy of the molecules in the energy con luminescent efficiency during the fabrication process. Other Verting region and the molecules quickly release the energy as multilayer structures may be used to improve the device per photons of light. The energy converting region can include formance (see, for example, U.S. Pat. No. 7,332,211 and U.S. poly(p-phenylene vinylene), polyfluorene, poly(fluorenylene Patent Application Publication No. 2004/0023010, each of ethynylene), poly(phenylene ethynylene), polyfluorene which is incorporated by reference in its entirety). A blocking vinylene, or polythiophene. The energy converting region can layer, such as an electron blocking layer (“EBL), a hole also include silicon, copper indium diselenide, Zinc oxide, blocking layer (“HBL) or a hole and electron blocking layer Zinc sulfide, Zinc selenide, Zinc telluride, cadmium oxide, (“eBL), can be introduced in the structure. A blocking layer cadmium sulfide, cadmium selenide, cadmium telluride, can include 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1, magnesium oxide, magnesium Sulfide, magnesium selenide, 2,4-triazole (“TAZ), 3,4,5-triphenyl-1,2,4-triazole, 3.5-bis magnesium telluride, mercuric oxide, mercuric sulfide, mer (4-tert-butylphenyl)-4-phenyl-1,2,4-triazole, bathocuproine curic selenide, mercuric telluride, aluminum nitride, alumi (BCP), 4,4',4'-tris {N-(3-methylphenyl)-N- num phosphide, aluminum arsenide, aluminum antimonide, phenylaminotriphenylamine (“m-MTDATA'), polyethyl gallium nitride, gallium phosphide, gallium arsenide, gallium ene dioxythiophene (“PEDOT), 1,3-bis(5-(4-dipheny antimonide, indium nitride, indium phosphide, indium ars lamino)phenyl-1,3,4-oxadiazol-2-yl)benzene, 2-(4- enide, indium antimonide, thallium nitride, thallium phos biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 1,3-bis phide, thallium arsenide, thallium antimonide, lead Sulfide, 5-(4-(1,1-dimethylethyl)phenyl)-1,3,4-oxadiazol-2-yl) lead selenide, lead telluride or combinations thereof. benzene, 1,4-bis(5-(4-diphenylamino)phenyl-1,3,4- 0148. The energy converting region can include two or oxadiazol-2-yl)benzene, O 1,3,5-tris(5-(4-(1,1- more layers of materials. The layers can be deposited on a dimethylethyl)phenyl)-1,3,4-oxadiazol-2-ylbenzene. surface of one of the electrodes by oxidative chemical vapor 0154 The applied voltage used for light generation can be deposition, spin coating, dip coating, vapor deposition, sput an AC voltage or DC voltage. A DC voltage can be supplied tering, or other thin film deposition methods. The layers can by DC voltage generator, including, for example, a battery, a include a p-type semiconductor and an n-type semiconductor. capacitor, or a rectified AC Voltage. An AC Voltage can be 014.9 The energy converting region can include an elec Supplied by an AC Voltage generator which produces a Volt troluminescent or emissive material. The electroluminescent age waveform, such as, for example, a square wave. The material can be selected for its emissive properties, such as waveform can have a frequency of between 0.01 Hz and 100 emission wavelength or line width. The electroluminescent kHz, 10 HZ and 1 MHz, 250 Hz, and 100 kHz, or 500 Hz, and material can be a wide band gap material. 10kHz. The average voltage can be between 2 and 15 volts, or 0150. The electrical properties (such as band gaps and 3 and 8 volts. The percentage of duty cycle used can be bandoffsets) of the energy converting region materials can be calculated as one hundred multiplied by the average Voltage selected in combination with the device structure to produce divided by the maximum Voltage. The percentage of duty a device where excitons are formed preferentially on the cycle can be the relative time in an on/off cycle (in 96) during emissive material. The emissive material can transfer energy which the Voltage is on. The frequency, duty cycle, and peak to an emission-altering material before light is emitted from Voltage can be adjusted to optimize light output and stability the device. Energy transfer can occur by emission of light from the device. Some applications of a duty cycle are from the emissive material and reabsorption by the emission described, for example, in G. Yuetal. Applied Physics Letters altering material. Alternatively, the energy transfer can be a 73:111-113 (1998), incorporated herein by reference in its US 2011/03 15204 A1 Dec. 29, 2011 entirety. For example, the AC voltage waveform can be a 50% conductivity was calculated assuming a constant film Volume duty cycle at 5V and 1 kHz, which has a maximum voltage of as described in the literature. (Hansen, T. S., West, K., Has 5 volts, a frequency of 1 kHz, and an average Voltage of 2.5 Sager, O., Larsen, N. B., Highly stretchable and conductive Volts. In this way, a low average operating Voltage can polymer material made from poly (3.4-ethylenediox improve the operating half-lives of the devices. ythiophene) and polyurethane elastomers. Adv. Funct. Mater. 17, 3069 (2007), which is incorporated by reference in its EXAMPLES entirety). The electrode adhesion on the PET and SaranTM Methods wrap substrates was also confirmed by tape testing (ASTM D3359-97), and the surface after flexing and stretching was (O155 Deposition of oCVD Polymer Electrodes. imaged using an Olympus CX41 optical microscope with a 0156 The oGVD process procedure and the reactor con figuration used have been previously described. (Baxamusa, maximum magnification of x100. Electrode foldability was S. H., Im, S. G., Gleason, K. K., Initiated and oxidative tested on ~100 nm oOVD PEDOT electrodes deposited on chemical vapor deposition: a scalable method for conformal untreated newsprint; the film thickness was based on films and functional polymer films on real substrates. Phys Chem deposited on glass slides from the same deposition. The fold Chem Phys 11,5227 (2009); Alf. M. E. et al., Chemical Vapor ing tests) (+180°) were performed by creasing the paper/ Deposition of Conformal, Functional, and Responsive Poly electrode flat using gentle pressure applied with a pencil mer Films. Adv. Mater. 22, 1993 (2010); and Im, S. G., eraser; for folding at +180°, the crease was made between two Gleason, K. K., Systematic control of the electrical conduc additional sheets of paper to prevent contact between the tivity of poly(3,4-ethylenedioxythiophene) via oxidative eraser and the polymer electrode. After each iteration, the chemical vapor deposition. Macromolecules 40, 6552 paper was completely flattened back to 0° and the sheet resis (2007), each of which is incorporated by reference in its tance was measured across the crease with a multimeter with entirety.) The same reaction conditions were used for all probe spacing of 1 cm (0.5 cm on either side of the crease). Substrates in this study. The Substrate temperature was main tained elevated at ~80°C. by a PID controller to help enhance OPV Device Fabrication. the film conductivity. (Im, S. G. (2007)). The process pres sure was maintained at ~100 mTorr. The flow rate of evapo 0158 Pre-patterned ITO/glass substrates were obtained rated 3,4-ethylenedioxythiophene monomer (Aldrich, 97%) from Thin Film Devices (sheet resistance=202D). The bare was metered at ~5 sccm and FeCl oxidant (Aldrich) was glass and the ITO/glass substrates were first cleaned by controllably evaporated from a resistively heated crucible at sequential 5 minute ultrasonications in deionized water/de -250° C. The thickness of OCVD PEDOT electrodes were tergent solution (Micro-90), deionized water, acetone, and determined by limiting the time of reaction (-5 min for a boiling isopropyl alcohol, and then exposed to oxygen plasma 50-nm thick film). OCVD PEDOT anodes were deposited for for 1 minute (100 W. Plasma Preen, Inc.). For the control thin film and OPV characterization on pre-cleaned glass (de devices, PEDOT:PSS solution (CLEVIOSTM PVP AI 4083) scribed below) and various other substrates, which were used was filtered (0.45 um), spin-coated at 4000 rpm for 60 sec as received: PET (5-mil Melinex R. Q65FA, Dupont), printer onds, annealed at 210°C. for 5 minutes in air, and finally paper (Office Depot, 201b, 92 brightness, #99964200), tissue exposed to oxygen plasma for <5 seconds (100 W. Plasma paper (Office Depot, #48601-OD), tracing paper (Canson, 25 Preen, Inc.). All substrates were then transferred to an evapo lb., #702-321), newsprint (Pacon Papers, #3407), Reynolds(R) ration chamber (<10 Torr) where the organic active layers Cut-Rite R. Wax Paper, and SaranTM Premium Wrap (SC (CuPc, Co, and BCP) and Ag cathodes were thermally Johnson). evaporated through a shadow mask at rates of ~1 AS', mea Sured using a calibrated quartz crystal microbalance. The Electrode Characterization. overlap area between the anode and cathode defined the device area which ranged from 0.005 to 0.01 cm. The copper O157 Electrode thickness was measured with a Tencor phthalocyanine (CuPc, Acros Organics, ca. 95% purity), P-16 profilometer and the sheet resistance was measured fullerene-Co (Co, Luminescence Technology Corp., >99. using a Signatone S-302-4 four-point probe station with a 5%) and bathocuprine (BCP, Sigma Aldrich, 99.99%) were Keithley 4200-SCS semiconductor characterization system. each purified once via thermal gradient Sublimation, and the The conductivity was calculated from the sheet resistance and Ag (Alfa Aesar, 1-3 mm shot, 99.9999%) was used as measured thickness. The optical transmission of the polymer received. electrodes was measured on glass using a Varian Cary 6000i UV-Vis-NIR spectrophotometer. Flex testing for ITO/PET OPV Device Characterization. (Aldrich, 5-mil PET with 1000 AITO, 602') and oCVD PEDOT electrodes on PET was performed using an in-house 0159. The J-V characteristics of the OPV cells were mea flexing-test system, and the sheet resistance was measured Sured in nitrogen atmosphere using a custom probe fixture between each flexing iteration. Stretch testing was performed with an Agilent 4156C Precision Semiconductor Parameter using a MTS Nano Instruments Nano-UTM nanotensile Analyzer and simulated AM 1.5 solar illumination from a tester. 5 mmx1 mm OCVD PEDOT electrodes on SaranTM Newport 91 1911 kW solar simulator. Opaque masks were wrap were anisotropically stretched by 0.01 mm increments used to selectively illuminate the active cell area, and optical at a strain rate of 0.005 s' while the resistance across the density filters were used to achieve the desired intensity as electrode (in the direction of extension) was simultaneously measured with a calibrated Siphotodiode. After testing, the measured using an Agilent U125A multimeterattached to the exact device areas were measured with an optical microscope polymer electrode using conductive tape and alligator clips. and used to calculate current density. Series and shunt resis The stretching extension was defined as the change in length tances were estimated as the inverse slope of the J-V curve at of the electrode divided the initial length (AL/Lo), and the V=+1.2V and OV, respectively. US 2011/03 15204 A1 Dec. 29, 2011 16

Results emitting from 350 to 1700 nm. The spectrometer was a Stel larNet EPP 2000 having a detector with a range spanning 190 Example 1 to 2200 nm. CVD Deposition and Characterization of PEDOT Example 2 Films Deposition on Fragile Substrates 0160 PEDOT depositions were carried out in a custom 0163 The conductive polymers have been deposited on a built vacuum chamber that has been described elsewhere and number of Substrates with no pre- or post-treatment, even a is depicted in FIG. 8. (D. D. Burkey, K. K. Gleason, J Appl ~10-um thick sheet of SARANTM wrap (FIG. 1b, left). In Phys 93,5143 (2003); H. G. Pryce-Lewis, D. J. Edell, K. K. contrast, drop-cast conducting polymer formulation CLEV Gleason, ChemMater 12,3488 (2000), which is incorporated IOSTM PH 750 (>650 S cm as a dried film) did not wet this by reference in its entirety). Glass slides and silicon wafers hydrophobic surface (FIG. 1b, right). While oxygen plasma were used for Substrates. The stage was regulated with cool pretreatment has been reported to enhance wettability, this ing water and was normally kept at 34°C. A stage heater was additional step can also add cost and can easily degrade the available when stage temperatures greater than room tem mechanical, chemical, and morphological properties of frag ile substrates. The conductive polymers also formed on sub perature were desired. The stage was also configured to be strates that would be destroyed or dissolved by solvents, such biased with a DC Voltage using a Sorenson DCS 600-1.7 as absorbent and water-soluble papers, (e.g. bathroom tissue power Supply. The chamber pressure was controlled by a and rice paper, respectively; FIGS. 5 and 6). butterfly valve connected to an MKS model 252-A exhaust valve controller and was maintained at approximately 300 Example 3 mTorr. Fe(III)Cl. (97%, Aldrich) was selected as the oxidant. The powder was loaded in a porous crucible with a nominal OCVD PEDOT Electrodes pore size of 7um and positioned above the stage. The crucible (0164 oCVD PEDOT (poly(3,4-ethylenediox was heated to a temperature of about 240° C., where subli ythiophene)) electrodes can Successfully replace the conven mation of the oxidant begins to occur. Argon (Grade 5.0, BOC tional indium tin oxide (ITO) anodes in organic photovoltaic Gases) was delivered into the crucible as a carrier gas for the devices (FIG. 2a, inset) fabricated with the well-studied Fe(III)Cl. Vapors. An argon flow rate of 2 sccm was set using CuPc/C/BCP/Ag molecular organic heterojunction archi an MKS mass flow controller with a range of 50 sccm N. tecture. (Peumans, P. Forrest, S. R., Very-high-efficiency Once a yellow film of Fe(III)C1 was observed on the sub double-heterostructure copper phthalocyanine/C-60 photo strate, the crucible temperature was reduced to end sublima voltaic cells. Appl. Phys. Lett. 79, 126 (2001); Schultes, S. tion. EDOT monomer (3,4-ethylenedioxythiophene, Aldrich) M., Sullivan, P., Heutz, S., Sanderson, B.M., Jones, T. S., The heated to 100°C. was then introduced into the reactor through role of molecular architecture and layer composition on the heated lines and using an MKS 1153 mass flow controller set properties and performance of CuPC-C-60 photovoltaic at 95°C. The EDOT flow rate was normally 10 sccm. Pyridine devices. Mater. Sci. Eng., C 25, 858 (2005); and Brumbach, (99%, Aldrich) at room temperature was evaporated into the M., Placencia, D., Armstrong, N. R., Titanyl phthalocyanine/ reactor using a needle valve to control the flow rate. A depo C-60 heterojunctions: Band-edge offsets and photovoltaic sition time of 30 minutes was used for all of the films. device performance.J. Phys. Chem. C 112,3142 (2008), each 0161. After deposition, the films were dried for at least 2 of which is incorporated by reference in it entirety). Impor hours in a vacuum oven heated to 80° C. at a gauge pressure tantly, all of the other device layers can also deposited at low of-15 in. Hg. The thickness of the films deposited on glass temperature and without the use of solvents, via vacuum was measured on a Tencor P-10 profilometer and conductiv thermal evaporation, allowing us to employ a versatile array ity measurements were done with a four-point probe (Model of substrates. To eliminate the possibility of performance MWP-6, Jandel Engineering, Ltd). Films on silicon sub variation due to fabrication conditions, all oCVD-based strates were measured with FTIR (Nexus 870, Thermo Elec devices were fabricated and tested in parallel with control tron Corporation) for information on chemical composition. devices, with structure ITO (100 nm)/PEDOT:PSS (70 nm)/ Deposited films were sometimes rinsed in methanol (HPLC CuPc (20 nm)/C (40 nm)/BCP (12 nm)/Ag (1000 nm). Grade, J. T. Baker) or in a 5 mM dopant solution of nitroso 0.165 FIG. 2a compares representative current density nium hexafluorophosphate, NOPF (96%, Alfa Aesar) in voltage (J-V) characteristics for OPVs on glass differing only acetonitrile (ACS Grade, EMT). The rinse step was intended in anode structure: (i) oCVD PEDOT, (ii) ITO, (iii) ITO/ to remove any unreacted monomer or oxidant in the films as oCVD PEDOT, (iv) ITO/PEDOT:PSS. The devices incorpo well as short oligomers and reacted oxidant remaining in the rating oCVD anodes (i and iii) performed comparably with form of Fe(II)Cl. After rinsing, the films changed from a the conventional anode structures (ii and iv), and both exhib cloudy light yellow color to a sky blue hue. ited improved open-circuit voltage relative to bare ITO. This 0162 Electrochemical testing took place in an aqueous Suggested that the oCVD layers can provide an advantageous 0.1M solution of sulfuric acid (VWR). The CVD PEDOT film work function and/or morphological benefit, analogous to on TTO was the working electrode, platinized copper was the behavior observed for PEDOT:PSS buffer layers. (Peumans, counter electrode, and a saturated calomel electrode (SCE) P. Forrest, S.R., Very-high-efficiency double-heterostructure was used as the standard. A potentiostat (EG&G Printon copper phthalocyanine/C-60 photovoltaic cells. Appl. Phys. Applied Research Model 263A) scanned from -0.4V to 0.6V Lett. 79, 126 (2001); Armstrong, N. R. et al., Interface modi based on preliminary cyclovoltammograms. In-situ UVNIS fication of ITO thin films: organic photovoltaic cells. Thin was conducted using an optical fiber to couple light from a Solid Films 445, 342 (2003); and Snaith, H. J., Kenrick, H., StellarNet SLI light source with a tungsten krypton bulb Chiesa, M., Friend, R. H. Morphological and electronic con US 2011/03 15204 A1 Dec. 29, 2011 sequences of modifications to the polymer anode PEDOT: films. (Ogasawara, M., Funahashi, K., Demura, T., Hagiwara, PSS. Polymer 46,2573 (2005), each of which is incorporated T., Iwata, K., Enhancement of Electrical-Conductivity of by reference in its entirety.) While both oCVD PEDOT and Polypyrrole by Stretching. Synth. Met. 14, 61 (1986); and PEDOT:PSS have comparable work functions (-5.2 eV) 15, Hansen, T. S., West, K., Hassager, O., Larsen, N. B., Highly the OCVD electrode was orders of magnitude more conduc stretchable and conductive polymer material made from poly tive than the PEDOT:PSS buffer layer (<10 S cm). Indeed, (3.4-ethylenedioxythiophene) and polyurethane elastomers. the ITO/oCVD PEDOT electrodes (iii) exhibited the highest Adv. Funct. Mater. 17, 3069 (2007), each of which is incor fill factor (>0.6) of the devices tested. This can be consistent porated by reference in its entirety). The conductivity then with a reduction in device series resistance relative to ITO/ slowly declined; however, significant electrical conductance PEDOT:PSS (iv) (Table 1). For the ITO-free oCVD elec was maintained until there was mechanical failure of the trodes (i), there was a trade-off between sheet resistance and underlying substrate at nearly 200%. This exceeded the transparency with thickness (FIG. 2b), which may account stretchability of typical metals, ITO, graphene, and even for the small differences in fill factor and short circuit current “wavy' silicon ribbons (electrical failure at ~5-30% exten relative to (ii) (Table 1). sion) and was comparable to some of the best reports for conducting polymer films and composites (electrical failure TABLE 1. at ~100-200% extension). (Cairns, D. R. et al., Strain-depen dent electrical resistance of tin-doped indium oxide on poly Solar cell parameters for OPVs with different anode layers. mer substrates. Appl. Phys. Lett. 76, 1425 (2000); Hansen, T. se V FI Rseries Rshunt S., West, K., Hassager, O., Larsen, N. B., Highly stretchable Anode Material (mA cm ) (V) Factor (S2 cm) (S2 cm) and conductive polymer material made from poly(3,4-ethyl OCVD PEDOT 3.2 O.44 OS4 S.O 0.8 x 10 enedioxythiophene) and polyurethane elastomers. Adv. ITO 4.4 O.41 O.S7 O.6 1.0 x 10 Funct. Mater. 17, 3069 (2007); Li, T., Huang, Z. Y., Suo, Z. ITO?oCVD PEDOT 4.1 O.48 O60 1.2 1.2 x 10 Lacour, S. P. Wagner, S., Stretchability of thin metal films on ITOPEDOT:PSS 4.2 O.47 O.S6 7.2 1.1 x 10 elastomer substrates. Appl. Phys. Lett. 85,3435 (2004); Kim, K. S. et al., Large-scale pattern growth of graphene films for 0166 Uniquely, oCVD conducting polymers can be in situ stretchable transparent electrodes. Nature 457, 706 (2009); covalently bonded (grafted) to flexible Substrates possessing Rogers, J. A. Someya, T., Huang, Y. G., Materials and aromatic functional groups upon film formation (e.g. on com Mechanics for Stretchable Electronics. Science 327, 1603; mon polystyrenes (PS) and polyethylene terephthalates Sekitani, T. etal. A rubberlike stretchable active matrix using (PET)). The superior adhesion of the grafted films can be elastic conductors. Science 321, 1468 (2008): Urdaneta, M. desirable for roll-to-roll processing and for flexible and G., Delille, R., Smela, E., Stretchable electrodes with high stretchable electronics, where mechanical stresses could oth conductivity and photo-patternability. Adv. Mater. 19, 2629 erwise result in catastrophic cracks or delamination. Indeed, (2007), each of which is incorporated by reference in its after 1000 flexing cycles at <5 mm radius (FIG. 3a), the entirety). Microscopic cracks gradually formed and became electrical conductivity of oCVD PEDOT on a PET substrate larger as the film was stretched, which interrupted the current was minimally affected while that of commercial ITO-coated conduction along the stretch direction; there were, however, PET decreased over 400-fold due to severe crack formation complete conducting polymer pathways visible even at 150% (FIG.3a, inset), a direct result of the brittle nature of the ITO extension (FIG. 3c, lower). and relatively weak substrate adhesion. (Cairns, D. R. et al., (0168 The foldability of oCVD PEDOT electrodes on Strain-dependent electrical resistance of tin-doped indium paper Substrates was demonstrated by repeatedly creasing the oxide on polymer substrates. Appl. Phys. Lett. 76, 1425 electrodes (FIG. 3d). After an initial decrease over the first (2000), which is incorporated by reference in its entirety). In -10 creases, the conductivity levels fell off at 50-150 S cm, contrast, the oCVD PEDOT exhibited no cracking and main and significant conductance was retained after over 100 fold tained its electrical conductivity even through extreme flexes ing iterations. This was in contrast to evaporated metal films, at a radius <1 mm. Moreover, after over 100 flexing cycles, which exhibited complete electrical failure after fewer than OPVs with oCVD PEDOT electrodes (i) on PET, displayed 10 folding iterations. (Siegel, A. C. et al., Foldable Printed no noticeable change in performance (FIG. 3b). Thus, the Circuit Boards on Paper Substrates. Adv. Funct. Mater. 20, 28 flexibility of the OCVD electrode may have allowed the sub (2010), which is incorporated by reference in its entirety). sequent device layer to retain its integrity upon flexing. This Moreover, conductivities on paper that are comparable to was strong contrast to reports for “flexible ITO-based OPVs planar films grown on glass Substrates during the same depo in which electrode cracking propagated through the device, sition cycle were observed. This was remarkable, considering ultimately resulting in shorting. (Na, S.I., Kim, S. S., Jo, J., theoCVD film thickness was much less than the RMS surface Kim, D. Y., Efficient and Flexible ITO-Free Organic Solar roughness of the paper (~2-4 um). The high conductivity of Cells Using Highly Conductive Polymer Anodes. Adv. Mater. oCVD PEDOT on such a highly non-planar surface and its 20, 4061 (2008), which is incorporated by reference in its endurance to repeated folding iterations may be rooted in the entirety). ability of the vapor-phase oCVD process to penetrate into the (0167. The stretchability of oCVD PEDOT electrodes was fibers of the paper substrate and create a partially conformal exhibited on common SaranTM wrap (~10-lum thick) (FIG. coating throughout the fiber matrix. This may impart good 3c). The oCVD PEDOT was also covalently bonded to this mechanical and electrical connectivity. PET-based Substrate, inhibiting slippage and ensuring that the 0169 OPVs were also fabricated directly on various as polymer electrode was stretched along with the substrate. purchased paper Substrates. The transparent polymer elec Under moderate stretching (up to 25% extension) the conduc trodes were conformally deposited on the delicate paper tivity steadily increases, most likely due to molecular chain fibers without any pretreatment steps or protecting layers. alignment, as has been reported for other conducting polymer The versatility of this ability can be hard to match by any other US 2011/03 15204 A1 Dec. 29, 2011 thin-film deposition technique. To help prevent electrical cations in OPV structures, oOVD polymers can be similarly shorting through the nonconformally evaporated active lay integrated in other large and Small-area optoelectronic device ers, the thickness of the CuPelayer was increased from 20 nm structures. Moreover, as the existing library of electrically to 100 nm. (Yang, F., Shtein, M., Forrest, S. R. Controlled and optically active oCVD polymer chemistries grows, the growth of a molecular bulk heterojunction photovoltaic cell. power of this technique may increase accordingly and it may Nature Mater. 4, 37 (2005), which is incorporated by refer be readily possible to make complete devices conformally on ence in its entirety.) The low transparency of the paper Sub complex and delicate substrates for novel architectures and strates along with the high CuPc absorption may have inhib ultimately improved performance. ited the intensity of light illuminating the OPV within an What is claimed is: exciton diffusion length of the photoactive heterojunction. 1. A light absorbing or emitting device comprising: Thus, for these devices the paper-substrates were illuminated a substrate with a textured surface; and with high-intensity 500 mW cm-simulated solar illumina a conductive polymer coating on a surface of the Substrate. tion to illuminate the photoactive interface as close as pos 2. The light absorbing or emitting device of claim 1, sible to intensities typical of OPVs on glass/ITO under 100 wherein the textured surface is porous or fibrous. mW cm illumination. Characteristic J-V performance 3. The light absorbing or emitting device of claim 1, curves (FIG. 4a) showed significant power generation for wherein the substrate is flexible. completed OPVs on tracing paper (b), tissue paper (c), and 4. The light absorbing or emitting device of claim 1, printer paper (d). The relatively low open-circuit Voltage as wherein the polymer coating is conformal to the Surface of the compared to the standard glass-based devices was likely a substrate. result of increased current pathways through the nonconfor 5. The light absorbing or emitting device of claim 2, mal photoactive layers that allow facile charge transport wherein the substrate is paper or cloth. opposite the photo-generated current. The short circuit cur 6. The light absorbing or emitting device of claim 1, rents scaled with Substrate transparency, which was expected; wherein the polymer coating includes monomeric units however, they were relatively high considering the absorptive derived from optionally substituted thiophenes, optionally Substrate and thick CuPe layer, Suggesting there may be substituted pyrroles or optionally substituted anilines. enhanced light utilization due to favorable scattering through 7. The light absorbing or emitting device of claim 6, the roughened Substrate and interfaces. wherein the polymer coating includes poly(3,4-ethylenediox (0170 The foldability of these devices as well as their ythiophene). ultra-light weight was evident. Ultrathin paper substrates 8. The light absorbing or emitting device of claim 1, (e.g., tissue paper) weigh ~10 g cm, in comparison to wherein the polymer coating includes at least one dopant. ~10 g cm' for a crystalline Siwafer and ~10° g cm' for 9. The light absorbing or emitting device of claim 1 further a conventional 5 mil PET plastic substrate. Although the comprising: efficiency of the ultrathin paper-based devices was lower than an electrode; and state-of-the-art solar modules, they exhibited high power-to an energy converting region capable of converting energy weight ratios of up to 550 W kg under these testing condi between photoenergy and electric energy. tions, and continued improvements in the cell efficiency may 10. The light absorbing or emitting device of claim 9. further extend their light-weight advantage. The devices were wherein the polymer coating is an anode and the electrode is also easily patterned over large areas and maintained photo a cathode. Voltaic power generation after folding into three-dimensional 11. The light absorbing or emitting device of claim 9. structures. FIG. 4g shows a thin-film photovoltaic cell inte wherein the energy converting region includes copper phtha grated into the wings of a paper airplane on a ~50 cm sheet of locyanine, fullerene-Co or bathocuprine. tracing paper that was first patterned with the oGVD-enabled 12. The light absorbing or emitting device of claim 9. device structure. The oCVD fabrication process was also wherein the energy converting region includes poly(p-phe compatible with other common papers, such as newsprint, nylene vinylene), polyfluorene, poly(fluorenylene ethy without disturbing the underlying printed ink (FIG. 4e), and nylene), poly(phenylene ethynylene), polyfluorene vinylene, even wax paper (FIG. 4f), which was resistant to or damaged or polythiophene. by common solvents. 13. The light absorbing or emitting device of claim 9. (0171 The nondestructive OCVD method enabled rapid wherein the energy converting region includes at least one fabrication of highly conductive, flexible, adherent, and material selected from the group consisting of silicon, copper transparent polymer electrodes from earth-abundant ele indium diselenide, Zinc oxide, Zinc sulfide, Zinc selenide, Zinc ments on virtually any Substrate, including delicate papers telluride, cadmium oxide, cadmium Sulfide, cadmium and plastics for large-area applications. Integration into OPV Selenide, cadmium telluride, magnesium oxide, magnesium structures resulted in ITO-free devices having comparable Sulfide, magnesium selenide, magnesium telluride, mercuric performance to control devices that utilize industry standard oxide, mercuric sulfide, mercuric selenide, mercuric tellu materials and processes. The versatility of the oGVD con ride, aluminum nitride, aluminum phosphide, aluminum ars ducting polymers was illustrated by organic Solar cells on a enide, aluminum antimonide, gallium nitride, gallium phos variety of as-purchased “everyday” paper Substrates, includ phide, gallium arsenide, gallium antimonide, indium nitride, ing printer paper, tissue paper, and tracing paper, fabricated indium phosphide, indium arsenide, indium antimonide, thal without any pretreatment steps or protecting layers, and lium nitride, thallium phosphide, thallium arsenide, thallium exhibiting power-to-weight ratios over 500 W kg. The antimonide, lead sulfide, lead selenide, or lead telluride. oCVD conducting polymer electrodes maintained their high 14. The light absorbing or light emitting device of claim 1, conductance even when flexed (>1000 times), creased (>100 wherein the device is a photovoltaic. times), and stretched (-200%), far exceeding the durability of 15. The light absorbing or light emitting device of claim 1, ITO and other standard electrode materials. Beyond the appli wherein the device is a light emitting diode. US 2011/03 15204 A1 Dec. 29, 2011

16. A light absorbing device comprising: 27. The light absorbing device of claim 24, wherein the a plastic Substrate; and energy converting region includes poly(p-phenylene a conductive polymer coating on a Surface of the Substrate. vinylene), polyfluorene, poly(fluorenylene ethynylene), poly 17. The light absorbing device of claim 16, wherein the (phenylene ethynylene), polyfluorene vinylene, or poly substrate is flexible. thiophene. 18. The light absorbing device of claim 16, wherein the surface of the substrate includes a plurality of functional 28. The light absorbing device of claim 24, wherein the groups. energy converting region includes at least one material 19. The light absorbing device of claim 18, wherein the selected from the group consisting of silicon, copper indium conductive polymer interacts with the plurality of functional diselenide, Zinc oxide, Zinc sulfide, Zinc selenide, Zinc tellu groups. ride, cadmium oxide, cadmium sulfide, cadmium selenide, 20. The light absorbing device of claim 19, wherein the cadmium telluride, magnesium oxide, magnesium sulfide, conductive polymer forms a covalent bond with the plurality magnesium selenide, magnesium telluride, mercuric oxide, of functional groups. mercuric Sulfide, mercuric selenide, mercuric telluride, alu 21. The light absorbing device of claim 16, wherein the minum nitride, aluminum phosphide, aluminum arsenide, polymer coating includes monomeric units derived from aluminum antimonide, gallium nitride, gallium phosphide, optionally substituted thiophenes, optionally Substituted pyr gallium arsenide, gallium antimonide, indium nitride, indium roles or optionally Substituted anilines. phosphide, indium arsenide, indium antimonide, thallium 22. The light absorbing device of claim 21, wherein the nitride, thallium phosphide, thallium arsenide, thallium anti polymer coating includes poly(3,4-ethylenedioxythiophene). monide, lead sulfide, lead selenide, or lead telluride. 23. The light absorbing device of claim 16, wherein the 29. The light absorbing device of claim 16, wherein the polymer coating includes at least one dopant. device is a photovoltaic. 24. The light absorbing device of claim 16, further com prising: 30. A method of making a light absorbing or light emitting an electrode; and device comprising: an energy converting region capable of converting energy providing a plastic or textured Substrate including a con between photoenergy and electric energy. ductive polymer on a Surface of the Substrate; and 25. The light absorbing device of claim 24, wherein the depositing an energy converting region capable of convert polymer coating is an anode and the electrode is a cathode. ing energy between photoenergy and electric energy on 26. The light absorbing device of claim 24, wherein the the substrate. energy converting region includes copper phthalocyanine, fullerene-Co or bathocuprine.