WO2011163556A2

WO2011163556A2 - Conductive polymer on a textured or plastic substrate

Info

Publication number: WO2011163556A2
Application number: PCT/US2011/041758
Authority: WO
Inventors: Karen K. Gleason; Vladimir Bulovic; Miles C. Barr; Jill A. Rowehl
Original assignee: Massachusetts Institute Of Technology
Priority date: 2010-06-24
Filing date: 2011-06-24
Publication date: 2011-12-29
Also published as: WO2011163556A3; EP2585543A2

Abstract

A conducting material can include a textured substrate and a conductive polymer coating on a surface of the substrate. The substrate can be flexible (e.g., paper or a flexible plastic) and the conducting properties of the material can withstand deformation of the substrate. Resilient and flexible devices can be formed on the substrate.

Description

CONDUCTIVE POLYMER ON A TEXTURED OR PLASTIC

SUBSTRATE

CLAIM OF PRIORITY

This application claims priority to U.S. Patent Application No. 12/822,691, filed June 24, 2010, and U.S. Patent Application No. 61/416,884, filed on November 24, 2010, each of which is incorporated by reference in its entirety.

GOVERNMENT SPONSORSHIP

This invention was made with government support under grant number

DGE0645960 awarded by the National Science Foundation. The government has certain rights in this invention.

TECHNICAL FIELD

This invention relates to a conductive polymer coating a surface of a textured or plastic substrate.

BACKGROUND

Conductive materials, such as conductive substrates, can be used to build structures with semiconductors to create useful devices. Semiconductors are materials that can contain either an excess of free electrons (N-type) or "holes" (P-type). N- and P- type materials can be joined to form diodes and transistors. Where the two films meet, negative charges can migrate across the junction to the positive side and vice versa, until an equilibrium is reached. This configuration can be used to create light emitting diodes ("LEDs") or photovoltaic ("PV") structures.

When a voltage is applied to an LED, a current flows through the junction in the form of electrons moving in one direction while holes move in the other direction. The migration of ionic charge across the junction causes a higher electrical potential than normal, which affects the way electrons combine with holes. When an electron combines with a hole, it can form an excited state pair, called an exciton, which can quickly release the energy as photons of light. Conversely, when a light of an appropriate wavelength is applied to a photovoltaic structure, photons are absorbed by the molecules, form excitons. The charges of the exciton can separate, moving toward opposite electrodes, thereby establishing a current.

SUMMARY

Semiconductors on common fiber-based papers and ultrathin plastics can be lightweight and foldable for storage and portability, easily shaped for three-dimensional applications, cut to size with scissors or torn by hand, and compatible with roll-to-roll manufacturing. However, such substrates can be easily damaged by common processing agents such as solvents, plasmas, or heat. Advantageously, a conductive polymer coating can be deposited on a substrate that can include a textured surface.

Versatile, substrate-independent, thin-film photovoltaics (PVs) can be prepared on a variety of ultra-lightweight "everyday" substrates (e.g., fiber-based papers; -0.001 g-cm^"2, and under 40 μιη in thickness) in addition to more common PV substrates (e.g., glass and plastic), all without any pretreatment and with identical processing. The ITO- free paper-thin PVs are possible with the use of highly deformable conducting-polymer electrodes (100-1000 S-cm^"1) that were synthesized, deposited, and vapor-patterned on each substrate in a single solvent-free step via oxidative chemical vapor deposition (oCVD). This allows monolithic fabrication of flexible and foldable, large-area, series- integrated PV circuits directly on common fibrous papers. These circuits produced over 50 V, were capable of powering common electronic displays under ambient lighting, and maintained significant power generation even after tortuous mechanical stressing and folding into large-area three-dimensional structures. Moreover, passive sub-micron encapsulation schemes significantly increased the lifetime of these organic-photovoltaic circuits without changing their paper- like qualities, while simultaneously enhancing functionality, such as water resistance.

In one aspect, a light absorbing or emitting device can include a substrate with a textured surface and a conductive polymer coating on a surface of the substrate.

In some embodiments, the textured surface can be porous or fibrous. In certain circumstances, the substrate can be paper or cloth. The substrate can be flexible. The polymer coating can be conformal to the surface of the substrate.

The polymer coating can include monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles or optionally substituted anilines. In some circumstances, the polymer coating can include poly(3,4- ethylenedioxythiophene). The polymer coating can include at least one dopant.

In some embodiments, the light absorbing or emitting device can further include an electrode and an energy converting region capable of converting energy between photoenergy and electric energy. The energy converting region can be positioned between the electrode and the polymer coating. The polymer coating can be an anode and the electrode can be a cathode.

In some embodiments, the energy converting region can include copper phthalocyanine, fullerene-C6o or bathocuprine. In some embodiments, the energy converting region can include poly(p-phenylene vinylene), polyfhiorene,

poly(fluorenylene ethynylene), poly(phenylene ethynylene), polyfhiorene vinylene, or polythiophene. In some embodiments, the energy converting region can include at least one material selected from the group consisting of: silicon, copper indium diselenide, zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium oxide, magnesium sulfide, magnesium selenide, magnesium telluride, mercuric oxide, mercuric sulfide, mercuric selenide, mercuric telluride, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, or lead telluride.

The device can further include an encapsulant encapsulating the device. The encapsulant can be waterproof.

In some embodiments, the light absorbing device can be a photovoltaic. In other embodiments, the light emitting device can be a light emitting diode.

In another aspect, a light absorbing device can include a plastic substrate and a conductive polymer coating on a surface of the substrate. In some embodiments, the substrate can be flexible.

In some embodiments, the surface of the substrate can include a plurality of functional groups. The conductive polymer can interact with the plurality of functional groups. The conductive polymer can form a covalent bond with the plurality of functional groups. In some embodiments, the polymer coating can include monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles or optionally substituted anilines. The polymer coating can include poly(3,4-ethylenedioxythiophene). The polymer coating can include at least one dopant.

In some embodiments, the light absorbing device can further include an electrode and an energy converting region capable of converting energy between photoenergy and electric energy.

In some embodiments, the polymer coating can be an anode and the electrode can be a cathode.

The device can further include an encapsulant encapsulating the device. The encapsulant can be waterproof. In some embodiments, the light absorbing device can be a photovoltaic.

In another aspect, a light absorbing or emitting device includes a plurality of individual light absorbing or emitting device elements arranged on a substrate with a textured surface, where each device element includes a conductive polymer coating on a surface of the substrate.

In another aspect, a method of making a light absorbing or light emitting device can include providing a plastic or textured substrate including a conductive polymer on a surface of the substrate and depositing an energy converting region capable of converting energy between photoenergy and electric energy on the substrate.

In another aspect, a method of making a light absorbing or light emitting device includes providing a plastic or textured substrate, depositing a conductive polymer on a surface of the substrate in a first predetermined pattern, depositing an energy converting region capable of converting energy between photoenergy and electric energy over the conductive polymer in a second predetermined pattern, and depositing an electrode material over the energy converting region in a third predetermined pattern.

The first predetermined pattern, the second predetermined pattern, and the third predetermined pattern can be selected together so as to form a plurality of individual device elements. The plurality of individual device elements can be electrically connected, such as, for example, in series, or in parallel, or in a combination of series and parallel connections.

The method can further include encapsulating the device. Encapsulating the device can include vapor deposition.

Depositing a conductive polymer on a surface of the substrate in a first predetermined pattern can include vapor deposition and the first predetermined pattern can be defined by a first mask. Depositing an energy converting region capable of converting energy between photoenergy and electric energy over the conductive polymer in a second predetermined pattern can include vapor deposition and the second predetermined pattern can be defined by a second mask.

Depositing an electrode material over the energy converting region in a third predetermined pattern can include vapor deposition and the third predetermined pattern can be defined by a third mask.

The energy converting region can include two or more layers of materials.

Other features, objects and advantages will be apparent from the description, the drawings, and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. la is a schematic of the oxidative chemical vapor deposition ("oCVD"). Fig. lb is a picture of poly(3,4-ethylenedioxythiophene) ("PEDOT") applied to SARAN™ wrap by two deposition techniques. Fig. 2a is a graph demonstrating the current-voltage ("J-V") characteristics for oCVD PEDOT-based organic photovoltaics ("OPVs") and conventional indium tin oxide ("ITO") based OPVs on rigid glass substrates. Fig. 2b is a graph showing the effect of oCVD film thickness on transmittance and inverse sheet resistance.

Fig. 3a is a graph demonstrating the conductivity with respect to flexing cycle for oCVD PEDOT film covalently bonded to a flexible polyethylene terephthalate ("PET") substrate and ITO-coated PET. Fig. 3b is a graph showing the J-V characteristics of an ITO-free OPV on PET before and after flexing cycles. Fig. 3c is a graph demonstrating the conductivity of an oCVD PEDOT electrode on SARAN™ wrap as it is

anisotropically stretched until substrate failure.

Fig. 3d is a graph demonstrating the conductivity of an oCVD PEDOT electrode on newsprint after repeated folding.

Fig. 4a is a graph showing the J-V performance characteristics of OPVs utilizing oCVD PEDOT electrodes on tracing paper (Fig. 4b), tissue paper (Fig. 4c), and printed paper (Fig. 4d). Fig. 4e shows a paper airplane with integrated photovoltaic wings folded from a sheet of tracing paper patterned with an oCVD-enabled device. Fig. 4f shows printed newspaper with an oCVD-enabled device. Fig. 4g shows wax paper with an oCVD-enabled device.

Fig. 5 a shows an oCVD polymer electrode on a single ply of bathroom tissue. Fig. 5b shows a single ply of bathroom tissue exposed to a drop-cast conducting polymer solution. Fig. 5c shows a measurement of the 2-point film resistance of an oCVD PEDOT electrode on a single ply of bathroom tissue.

Fig. 6a shows rice paper with an oCVD polymer electrode. Fig. 6b shows rice paper after being exposed to a drop-cast conducting polymer. Fig. 6c shows a

measurement of the 2-point film resistance of an oCVD PEDOT electrode on rice paper.

Fig. 7 shows a conductive polymer conforming to fibers of substrates.

Fig. 8 shows the oCVD system.

Fig. 9 illustrates exemplary configurations including a conducting material.

Fig. 10a is a schematic diagram of the oCVD process. Fig. 10b is a photograph of a 200 nm-thick PEDOT film vapor patterned on tissue paper in 15 pt. bold Verdana font. Fig. 10c shows the effect of oCVD PEDOT film thickness on transmittance at 630 nm (circles) and inverse sheet resistance (squares). Fig. lOd displays normalized conductivity with respect to mechanical deformations of as-deposited 50-nm thick oCVD PEDOT films on various substrates: repeated flexing on PET to radius <5 mm (labeled flexes), repeated folds to a crease on newsprint (labeled folds), and anisotropic stretching until substrate failure on Saran™ wrap (~10-μιη thick) (labeled stretch). The flexing experiment is also shown for ITO on PET for reference (dashed line). All PEDOT conductivities started between 100-1000 S-cm^"2.

Fig. 11a is a schematic depiction of PV device architecture; C₆o was utilized as the acceptor unless otherwise noted. Figs. 1 lb- 1 Id are graphs showing J-V performance characteristics for devices on glass (Fig. lib), differing only in anode structure (ii and iv are for reference and do not include oCVD PEDOT), PET after repeated flexes to 5 mm radius (Fig. 11c), and various papers (Fig. l id). Fig. lie shows internal and external quantum efficiency comparison for PVs on glass/ITO (black) and paper/oCVD PEDOT. The right-hand panel shows the corresponding completed devices on various substrates: PET (5-mil thick) (Fig. 1 If), copy paper (~120-μιη thick) (Fig. l lg), tracing paper (-40- μιη thick) (Fig. llh), and tissue paper (~40-μιη thick) (Fig. Hi). Functioning devices were also made on other common papers, including wax paper (Fig. llj), which is resistant to many solvents, as shown by the droplet of conducting polymer solution (CLEVIOS™ PH 750), which beads up on the completed device; and pre-printed newspaper (Fig. 1 lk), without disturbing the underlying ink. Devices maintained power generation after folding into three-dimensional structures; Fig. Ill shows a paper airplane with integrated photovoltaic wings, folded from a -50 cm² sheet of tracing paper that was first patterned with the oCVD-based device structure (inset).

Fig. 12a is a graph showing J-V performance curves for series-integrated PVs with vapor-patterned oCVD electrodes on paper and glass. Fig. 12b is a map of individual cell open-circuit voltages across the respective 7x7 cm² PV circuits. The lower insets show the cumulative fraction of devices producing at or below a given voltage. Fig. 12c is a series of photographs of a paper PV circuit progressively folded in air while maintaining high voltages at AM 1.5, 80 mW-cm^"2. The final folded structure can be dynamically unfolded and refolded without loss of performance in each three-dimensional

configuration.

Fig. 13 shows passive thin-film packaging schemes for paper PV circuits. Fig. 13a is a graph showing normalized efficiency of thin-film-packaged and unpackaged paper PV circuits (250 series-integrated cells) subjected to constant illumination (80 mW-cm^"2, halogen lamp) in air at 42 °C (108 °F) as a function of time. Fig. 13b shows photographs of a laminated paper PV circuit (128-series integrated cells) powering an LCD clock in air with ambient light. The left image shows the clock' s circuitry, which is powered by the PV alone and regulates a constant voltage to the display for changes in light intensity. Fig. 13c shows an iCVD PFDA-coated (400 nm) paper PV circuit (28-series integrated cells) submerged in water without significant loss in power generation. The inset shows a nearly spherical droplet of water on the surface of the paper circuit. Fig. 13d shows the same circuit after tortuous roll-to-roll processing by an office laser-jet printer, and that the circuit maintained efficiency sufficient to power the LCD display.

Fig. 14 is a photograph of patterned PEDOT films deposited by oCVD on different materials. From top, PET, Saran™ Wrap, tracing paper, and tissue paper.

Figs. 15a-15d are photomicrographs of materials on flexible substrates shown after flexing. 15a, oCVD PEDOT on PET; 15b, ITO on PET; 15c, oCVD PEDOT (full device) on PET; 15d, ITO (full device) on PET. Figs. 15e-15f are graphs showing the variation in height across the samples shown in Figs. 15c and 15d, respectively.

Fig. 16 is a series of optical microscope images of a 50-nm thick oCVD PEDOT electrode on Saran™ wrap (~10-μιη thick) after varying degrees of anisotropic stretching.

Figs. 17a- 17g are graphs depicting optical properties of different materials.

Fig. 18 presents graphs illustrating optical properties of a device.

Fig. 19 presents graphs illustrating optical properties of a device.

Fig. 20 is a schematic representation of patterns used in forming a large-area device.

Figs. 21a-21b are graphs showing device performance over time for devices with different packaging structures.

Figs. 22a-22c are a series of photographs illustrating the flexibility and performance of a packaged device.

Figs. 23a-23b are graphs showing measurements obtained from oCVD vapor- printed polymer electrodes. Fig. 23a demonstrates a relationship between transmittance (550 nm) and sheet resistance for the vapor-printed oCVD PEDOT used in the work. The thick line is a fit to equation (1) giving odc/oop=9 (the dashed black line is for reference and corresponds to odc/oop=35, representative for traditional metal oxide electrodes). The lower inset includes sheet resistance plotted versus film thickness. The upper inset includes 200-nm thick PEDOT film vapor printed on tissue paper in 15 pt. bold Verdana font. Fig. 23b demonstrates current density- voltage characteristics for organic oCVD PEDOT PVs on glass differing only in anode structure. The inset shows the device structure used in the work; C60 was utilized as the acceptor unless otherwise noted.

DETAILED DESCRIPTION

There is a need for development of conducting polymers deposited directly on substrates that are inexpensive, widely available, and compatible with high-throughput manufacturing. In addition, conducting polymers, for example in photovoltaics, on common paper, plastic, or fiber substrates could be seamlessly integrated into existing products (e.g. wall paper, window curtains, newspapers, clothing, etc.). Existing synthesis techniques for conducting polymers can preclude their deposition on some substrates like paper or on top of other materials that are incompatible with solutions- based processing. This fact can limit their application in electronic devices, such as photovoltaics ("PVs") or light emitting diodes ("LEDs"), as a bottom-electrode layer or as a coating on a bottom electrode to facilitate better hole injection. For example, conventional transparent electrodes (e.g. indium tin oxide) can be deposited via sputtering, which is not compatible with processing-sensitive substrates. Progress has been made in the development of solution-processable materials for large-area printing of flexible photovoltaics; however, solution wettability and solvent compatibility requirements can limit substrate choices. The development of a robust vapor-deposition technique for conducting polymers that preserves their high conductivity and is compatible with moisture-sensitive, temperature-sensitive, and mechanically fragile surfaces is needed to broaden their utilization, enabling both improved efficiencies in existing devices and development of new devices on unconventional substrates.

In 1977, the field of conducting polymeric materials, also known as synthetic metals, began with the discovery that polyacetylene conducts electricity. (H. Shirakawa, E. J. Louis, A. G. Macdiarmid, C. K. Chiang, and A. J. Heeger, "Synthesis of Electrically Conducting Organic Polymers-Halogen Derivatives of Polyacetylene, (Ch)X," Journal of the Chemical Society-Chemical Communications 16, 578-580 (1977), which is incorporated by reference in its entirety). Efforts to incorporate conducting polymers into electronic devices, including light-emitting diodes (LEDs), electrochromic materials and structures, microelectronics, portable and large-area displays, and photovoltaics have continued since that time. (C. T. Chen, "Evolution of red organic light-emitting diodes: Materials and devices," Chemistry of Materials 16(23), 4389-4400 (2004); A. P. Kulkarni, C. J. Tonzola, A. Babel, and S. A. Jenekhe, "Electron transport materials for organic light-emitting diodes," Chemistry of Materials 16(23), 4556-4573 (2004); A. A. Argun, P. H. Aubert, B. C. Thompson, I. Schwendeman, C. L. Gaupp, J. Hwang, N. J. Pinto, D. B. Tanner, A. G. MacDiarmid, and J. R. Reynolds, "Multicolored electrochromism polymers: Structures and devices," Chemistry of Materials 16(23), 4401-4412 (2004); D. K. James and J. M. Tour, "Electrical measurements in molecular electronics," Chemistry of Materials 16(23), 4423-4435 (2004); C. R. Newman, C. D. Frisbie, D. A. da Silva, J. L. Bredas, P. C. Ewbank, and K. R. Mann, "Introduction to organic thin film transistors and design of n-channel organic semiconductors," Chemistry of Materials 16(23), 4436-4451 (2004); M. L. Chabinyc and A. Salleo, "Materials requirements and fabrication of active matrix arrays of organic thin-film transistors for displays," Chemistry of Materials 16(23), 4509-4521 (2004); and K. M. Coakley and M. D. McGehee, "Conjugated polymer photovoltaic cells," Chemistry of Materials 16(23), 4533-4542 (2004), each of which is incorporated by reference in its entirety.)

Polymers, such as polyphenylene, polyaniline, polythiophene, polypyrrole, polycarbazole, or polysilane, can have delocalized electrons along their backbones enabling charge conduction. The conductivity can increase when anions present as dopants in the polymer matrix stabilize positive charges along the chain. Each of the conducting polymers can be substituted with a variety of functional groups to achieve different properties, so new derivatives continue to be synthesized. (J. L. Bredas and R. J. Silbey, Conjugated polymers: the novel science and technology of highly conducting and nonlinear optically active materials (Kluwer Academic Publishers, Dordrecht; Boston, 1991), pp. xviii, 624 p.; and T. A. Skotheim, R. L. Elsenbaumer, and J. R. Reynolds, Handbook of conducting polymers, 2nd ed. (M. Dekker, New York, 1998), pp. xiii, p. 1097, each of which is incorporated by reference in its entirety.)

One conducting polymer can bepoly-3,4-ethylenedioxy-thiophene (PEDOT) developed by scientists at Bayer AG in Germany. (Bayer, Eur. Patent 339340 (1988); B. L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. Reynolds, "Poly(3,4- ethylenedioxythiophene) and its derivatives: Past, present, and future," Advanced Materials 12(7), 481-494 (2000); and F. Jonas and L. Schrader, "Conductive

Modifications of Polymers with Polypyrroles and Polythiophenes," Synthetic Metals

41(3), 831-836 (1991), each of which is incorporated by reference in its entirety.) It was initially designed to block the β-positions on the thiophene ring to prevent undesirable side reactions. The strategy worked and the ethylene bridge on the molecule can act as a good charge donor to the π-conjugated backbone, giving rise to an unusually high conductivity of 300 S/cm. (G. Heywang and F. Jonas, "Poly(Alkylenedioxythiophene)S— New, Very Stable Conducting Polymers," Advanced Materials 4(2), 116-118 (1992), which is incorporated by reference in its entirety). In addition, PEDOT films in their oxidized state can be extremely stable for conducting polymers and nearly transparent. (M. Dietrich, J. Heinze, G. Heywang, and F. Jonas, "Electrochemical and Spectroscopic Characterization of Poly alky lenedioxythiophenes," Journal of Electroanalytical

Chemistry 369(1-2), 87-92 (1994), which is incorporated by reference in its entirety). However, like other conjugated polymers that have a very rigid conformation in order to maintain electron orbital overlap along the backbone, PEDOT can be insoluble. Bayer addressed this problem by using a water soluble polyanion, polystyrene sulfonic acid (PSS), during polymerization as the charge -balancing dopant. The PEDOT:PSS system is marketed as BAYTRON P™ and it has good film forming capabilities, a conductivity of 10 S/cm, good transparency, and extremely good stability. In fact, the films can be heated in air over 100 °C for over 1000 hours with no major decline in conductivity.

Studies demonstrate that Bayer's BAYTRON P materials (PEDOT stabilized with polystyrene sulfonate) can have increased conductivity up to 600 S/cm by adding N- methyl-pyrolidone (NMP) or other solvents that reduce screening effects of the polar solvent between the dopant and the polymer main chain. (F. Louwet, L. Groenendaal, J. Dhaen, J. Manca, J. Van Luppen, E. Verdonck, and L. Leenders, "PEDOT/PSS: synthesis, characterization, properties and applications," Synthetic Metals 135(1-3), 115-117 (2003); and J. Y. Kim, J. H. Jung, D. E. Lee, and J. Joo, "Enhancement of electrical conductivity of poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) by a change of solvents," Synthetic Metals 126(2-3), 311-316 (2002), each of which is incorporated by reference in its entirety.) Bayer's first major customer for BATRON P was Agfa who used the material as an anti-static coating on photographic film. (F. Jonas, W. Kraffi, and B. Muys, "Poly(3,4-Ethylenedioxythiophene)-Conductive Coatings, Technical Applications and Properties," Macromolecular Symposia 100, 169-173 (1995); Bayer, European Pat 440957 (1991); and Agfa, European Patent 564911 (1993), each of which is incorporated by reference in its entirety.) Any spark generated by static electricity can expose film showing up as a bright spot on developed photos. Bayer has since enjoyed utilization of BAYTRON P as an electrode material in capacitors and a material for through-hole plating of printed circuit boards. (F. Jonas and J. T. Morrison, "3,4- polyethylenedioxythiophene (PEDT): Conductive coatings technical applications and properties," Synthetic Metals 85(1-3), 1397-1398 (1997); Bayer, European Patent 533671 (1993); Bayer, European Patent 686662 (1995); Bayer, U.S. Pat. No. 5,792,558 (1996); and F. Jonas and G. Heywang, "Technical Applications for Conductive Polymers," Electrochimica Acta 39(8-9), 1345-1347 (1994), each of which is incorporated by reference in its entirety.) BAYTRON P can also be suitable as a hole-injecting layer in LEDs and photo vol taics, increasing device efficiency by up to 50%. (T. M. Brown, J. S. Kim, R. H. Friend, F. Cacialli, R. Daik, and W. J. Feast, "Built-in field electroabsorption spectroscopy of polymer light-emitting diodes incorporating a doped poly(3,4-ethylene dioxythiophene) hole injection layer," Applied Physics Letters 75(12), 1679-1681 (1999); and G. Greczynski, T. Kugler, M. Keil, W. Osikowicz, M. Fahlman, and W. R. Salaneck, "Photoelectron spectroscopy of thin films of PEDOT-PSS conjugated polymer blend: a mini-review and some new results," Journal of Electron Spectroscopy and Related Phenomena 121(1-3), 1-17 (2001), each of which is incorporated by reference in its entirety.)

Conducting polymer materials can be formed via oxidative polymerization of aniline, pyrrole, thiophene, or their derivatives. (A. Malinauskas, "Chemical deposition of conducting polymers," Polymer 42(9), 3957-3972 (2001), which is incorporated by reference in its entirety). In general, it has not been feasible to process bulk material of these polymers into thin films since they can be insoluble and non-melting, but coating techniques have been developed on substrates including plastic, glass, metal, fabric and micro- and nano-particles. Four main approaches can be utilized to form coatings of anilines, pyrroles, or thiophenes via oxidative polymerization on various materials:

electropolymerization of monomers at electrodes, casting a solution of monomer and oxidant on a surface and allowing the solvent to evaporate, immersing a substrate in a solution of monomer and oxidant during polymerization, and chemical oxidation of a monomer directly on a substrate surface that has been enriched with an oxidant.

Historically, electrochemical oxidation on different electrode materials has been the primary route to conducting polyaniline, polypyrrole films, polythiophene, and their derivatives. (E. M. Genies, A. Boyle, M. Lapkowski, and C. Tsintavis, "Polyaniline— a

Historical Survey," Synthetic Metals 36(2), 139-182 (1990); L. X. Wang, X. G. Li, and Y. L. Yang, "Preparation, properties and applications of polypyrroles," Reactive &

Functional Polymers 47(2), 125-139 (2001); E. Smela, "Microfabrication of PPy microactuators and other conjugated polymer devices," Journal of Micromechanics and Microengineering 9(1), 1-18 (1999); Q. B. Pei, G. Zuccarello, M. Ahlskog, and O.

Inganas, "Electrochromic and Highly Stable Poly(3,4-Ethylenedioxythiophene) Switches between Opaque Blue-Black and Transparent Sky Blue," Polymer 35(7), 1347-1351 (1994); R. Kiebooms, A. Aleshin, K. Hutchison, and F. Wudl, "Thermal and

electromagnetic behavior of doped poly(3,4-ethylenedioxythiophene) films," Journal of Physical Chemistry B 101(51), 11037-11039 (1997); A. M. White and R. C. T. Slade, "Electrochemically and vapour grown electrode coatings of poly(3,4- ethylenedioxythiophene) doped with heteropoly acids," Electrochimica Acta 49(6), 861- 865 (2004); and A. Aleshin, R. Kiebooms, R. Menon, F. Wudl, and A. J. Heeger,

"Metallic conductivity at low temperatures in poly(3,4-ethylenedioxythiophene) doped with PF6," Physical Review B 56(7), 3659-3663 (1997), each of which is incorporated by reference in its entirety.) Deposition can take place on an inert electrode material, which can be platinum, but can also be iron, copper, zinc, chrome-gold, lead, palladium, different types of carbon, semiconductors, or on transparent electrodes like indium tin oxide. (D. W. Deberry, "Modification of the Electrochemical and Corrosion Behavior of Stainless-Steels with an Electroactive Coating," Journal of the Electrochemical Society 132(5), 1022-1026 (1985); G. Mengoli, M. M. Musiani, B. Pelli, and E. Vecchi, "Anodic Synthesis of Sulfur-Bridged Polyaniline Coatings onto Fe Sheets," Journal of Applied Polymer Science 28(3), 1125-1136 (1983); and G. Mengoli, M. T. Munari, and C.

Folonari, "Anodic Formation of Polynitroanilide Films onto Copper," Journal of Electroanalytical Chemistry 124(1-2), 237-246 (1981), each of which is incorporated by reference in its entirety). Electrochemical oxidation can take place in an acidic electrolytic solution having anions like chloride, sulfate, fluorosulfonates, and hexafluorophosphate. Deposition can occur as the potential of the electrode is cycled in a range of around -0.6 V to 1 V. Aniline and pyrrole polymerized electrochemically can have conductivities ranging as high as 10 S/cm. Electrochemically deposited

polythiophenes, especially the PEDOT derivative, can reach conductivities that are an order of magnitude higher, around 200 to 300 S/cm. (H. Yamato, K. Kai, M. Ohwa, T. Asakura, T. Koshiba, and W. Wernet, "Synthesis of free-standing poly(3,4- ethylenedioxythiophene) conducting polymer films on a pilot scale," Synthetic Metals 83(2), 125-130 (1996), which is incorporated by reference in its entirety.) Using a variety of heteropolyacids as dopants in the electrolyte solution can enable the formation of free- standing films as opposed to coatings on electrodes. Although electrochemical polymerization can produce films that may not be processible, it can have an advantage of making a clean product that does not need to be extracted from a solution. The experimental setup can also be coupled to physical spectroscopic techniques like visible, IR, Raman, and ellipsometry for in-situ characterization.

Chemical oxidation of unsubstituted or substituted aniline, pyrrole, or thiophene can also take place in solution in the presence of an oxidant, for example, iron(III) chloride, iron(III) tosylate, hydrogen peroxide, potassium iodate, potassium chromate, ammonium sulfate, or tetrabutylammonium persulfate (TBAP). (A. Yasuda and T.

Shimidzu, "Chemical Oxidative Polymerization of Aniline with Ferric-Chloride,"

Polymer Journal 25(4), 329-338 (1993); R. Corradi and S. P. Amies, "Chemical synthesis of poly(3,4-ethylenedioxythiophene)," Synthetic Metals 84(1-3), 453-454 (1997); T. Yamamoto and M. Abla, "Synthesis of non-doped poly(3,4-ethylenedioxythiophene) and its spectroscopic data," Synthetic Metals 100(2), 237-239 (1999); F. Tran-Van, S.

Garreau, G. Louarn, G. Froyer, and C. Chevrot, "Fully undoped and soluble oligo(3,4- ethylenedioxythiophene)s: spectroscopic study and electrochemical characterization," Journal of Materials Chemistry 11(5), 1378-1382 (2001); D. Hohnholz, A. G.

MacDiarmid, D. M. Sarno, and W. E. Jones, "Uniform thin films of poly-3,4- ethylenedioxythiophene (PEDOT) prepared by in-situ deposition," Chemical

Communications (23), 2444-2445 (2001); A. Pron, F. Genoud, C. Menardo, and M.

Nechtschein, "The Effect of the Oxidation Conditions on the Chemical Polymerization of Polyaniline," Synthetic Metals 24(3), 193-201 (1988); M. Angelopoulos, G. E. Asturias, S. P. Ermer, A. Ray, E. M. Scherr, A. G. Macdiarmid, M. Akhtar, Z. Kiss, and A. J. Epstein, "Polyaniline-Solutions, Films and Oxidation-State," Molecular Crystals and Liquid Crystals 160, 151-163 (1988); Y. Cao, A. Andreatta, A. J. Heeger, and P. Smith, "Influence of Chemical Polymerization Conditions on the Properties of Polyaniline," Polymer 30(12), 2305-2311 (1989); J. C. Chiang and A. G. Macdiarmid, "Polyaniline- Protonic Acid Doping of the Emeraldine Form to the Metallic Regime," Synthetic Metals 13(1-3), 193-205 (1986); and I. Kogan, L. Fokeeva, I. Shunina, Y. Estrin, L. Kasumova, M. Kaplunov, G. Davidova, and E. Knerelman, "An oxidizing agent for aniline polymerization," Synthetic Metals 100(3), 303-303 (1999), each of which is incorporated by reference in its entirety.) The presence of the strongest of the acid anions (e.g., chloride) in the oxidant can result in the highest conductivities. Chemical oxidation can produce polymers with conductivities comparable to electrochemically deposited films using the same oxidant. (J. A. Walker, L. F. Warren, and E. F. Witucki, "New Chemically Prepared Conducting Pyrrole Blacks," Journal of Polymer Science Part a-Polymer Chemistry 26(5), 1285-1294 (1988), which is incorporated by reference in its entirety.) Generally, polar solvents like alcohols or acetonitrile can be used and reactions can take place over a range of oxidant concentrations and temperatures including 0 to 80°C, under acidic or basic conditions. (L. Yu, M. Borredon, M. Jozefowicz, G. Belorgey, and R. Buvet, Journal of Polymer Science Part A-Polymer Chemistry 10, 2931 (1987), which is incorporated by reference in its entirety). However, these parameters can influence the yield of polymerization and the conductivity of the final product. Solution-based chemical oxidation can produce powder precipitates that are packed into the form of a tablet and then characterized since they are generally insoluble and do not melt. The polymerized material can be rinsed in water, methanol, or acetonitrile to remove unreacted oxidant. Improved conductivities can be obtained after rinsing the material in a solution containing anionic dopants like

hydrochloric acid (HC1) or dissolved nitrosonium hexafluorophosphate (NOPF₆).

Chemical polymerization of aniline or pyrrole can result in conductivities as high as 10 or 50 S/cm, although using TBAP was reported to give polyaniline with a conductivity of 400 S/cm. PEDOT can often have a conductivity of up to 200 or 300 S/cm. A film with these materials can be formed by immersing a substrate in the reaction solution during polymerization.

Polyaniline can also be synthesized via the Ullmann reaction using p- bromoaniline as a precursor, but a low conductivity of only 10^"6 S/cm was measured. (F. Ullmann, Ber Dtsch Chem Ges 36, 2382-2384 (1903), which is incorporated by reference in its entirety). Interfacial polymerization of pyrrole using an aqueous oxidant solution and an organic phase with dissolved monomer can achieve free-standing thin films with conductivities of as high as 50 S/cm. (M. Nakata, M. Taga, and H. Kise, "Synthesis of Electrical Conductive Polypyrrole Films by Interphase Oxidative Polymerization-Effects of Polymerization Temperature and Oxidizing- Agents," Polymer Journal 24(5), 437-441 (1992), which is incorporated by reference in its entirety.)

Dipping a substrate material into a solution containing oxidants like FeCl₃ or Fe(OTs)3 and allowing it to dry can yield an oxidant-enriched substrate that can provide a reactive surface that polymerizes volatile monomers including aniline, pyrrole, thiophene, or their derivatives. (B. Winther- Jensen, J. Chen, K. West, and G. Wallace, "Vapor phase polymerization of pyrrole and thiophene using iron(III) sulfonates as oxidizing agents," Macromolecules 37(16), 5930-5935 (2004); J. Kim, E. Kim, Y. Won, H. Lee, and K. Suh, "The preparation and characteristics of conductive poly(3,4-ethylenedioxythiophene) thin film by vapor-phase polymerization," Synthetic Metals 139(2), 485-489 (2003); and B. Winther- Jensen and K. West, "Vapor-phase polymerization of 3,4- ethylenedioxy thiophene: A route to highly conducting polymer surface layers,"

Macromolecules 37(12), 4538-4543 (2004), each of which is incorporated by reference in it entirety.) A conductivity of 50 S/cm can be achieved using this method for polypyrrole and 500 to 1000 S/cm has been reported for PEDOT. Oxidant pretreatment can be extended to glass substrates, polymers, fabrics, and even individual fibers. (S. N. Tan and H. L. Ge, "Investigation into vapour-phase formation of polypyrrole," Polymer 37(6), 965-968 (1996); A. Mohammadi, I. Lundstrom, and O. Inganas, "Synthesis of Conducting Polypyrrole on a Polymeric Template," Synthetic Metals 41(1-2), 381-384 (1991); and C. C. Xu, P. Wang, and X. T. Bi, "Continuous Vapor-Phase Polymerization of Pyrrole .1. Electrically Conductive Composite Fiber of Polypyrrole with Poly(P-Phenylene

Terephthalamide)," Journal of Applied Polymer Science 58(12), 2155-2159 (1995).] Pretreating a surface with iodine vapors can present a solvent- less polymerization process for polypyrrole, but only low conductivities ranging from 10.sup.-7 to 10. sup. -1 S/cm result. [S. L. Shenoy, D. Cohen, C. Erkey, and R. A. Weiss, "A solvent-free process for preparing conductive elastomers by an in situ polymerization of pyrrole," Industrial & Engineering Chemistry Research 41(6), 1484-1488 (2002), each of which is incorporated by reference in its entirety.)

Another solvent-less deposition process has been demonstrated for polypyrrole that eliminates the step of dip-coating a substrate in an oxidant solution, although it can be restricted to metallic substrates. The surface of metals including copper, iron, gold, and/or palladium can be converted into salts by exposing them to vapors of chlorine, iodine, or bromine and acids with F^", NO₃ ^", SO₄ ^2", or CIO₄ ^" anions. Subsequent introduction of monomer vapor can result in polymer films with conductivities of around 1 to 10 S/cm. (G. Serra, R. Stella, and D. De Rossi, "Study of the influence of oxidising salt on conducting polymer sensor properties," Materials Science & Engineering C- Biomimetic Materials Sensors and Systems 5(3-4), 259-263 (1998); A. Nannini and G. Serra, "Growth of Polypyrrole in a Pattern— a Technological Approach to Conducting Polymers," Journal of Molecular Electronics 6(2), 81-88 (1990); F. Cacialli and P.

Bruschi, "Site-selective chemical-vapor-deposition of submicron-wide conducting polypyrrole films: Morphological investigations with the scanning electron and the atomic force microscope," Journal of Applied Physics 80(1), 70-75 (1996); and P.

Bruschi, F. Cacialli, A. Nannini, and B. Neri, "Low-Frequency Resistance Fluctuation Measurements on Conducting Polymer Thin-Film Resistors," Journal of Applied Physics 76(6), 3640-3644 (1994), each of which is incorporated by reference in its entirety.)

Vacuum deposition of polyaniline films using evaporation can yield conductivities of about 10^"4 S/cm. (T. L. Porter, K. Caple, and G. Caple, "Structure of Chemically Prepared Freestanding and Vacuum-Evaporated Polyaniline Thin-Films," Journal of Vacuum Science & Technology a- Vacuum Surfaces and Films 12(4), 2441-2445 (1994); and T. R. Dillingham, D. M. Cornelison, and E. Bullock, "Investigation of Vapor- Deposited Polyaniline Thin- Films," Journal of Vacuum Science & Technology a- Vacuum Surfaces and Films 12(4), 2436-2440 (1994), each of which is incorporated by reference in its entirety.) Solid polyaniline can be sublimed at temperatures of about 400°C and pressures of 10^"5 or 10^"6 Torr. Compositional analysis using XPS can show a carbon-to- nitrogen ratio of about 6:1 for the source material. A slightly higher C/N ratio in the deposited film can indicate that short oligomers preferentially sublime.

Plasma-enhanced chemical vapor deposition (PECVD) can be another method of depositing aniline, thiophene or parylene-substituted precursors. However, PECVD can yield low conductivities of only 10^"4 S/cm due to ring breakage or other imperfections caused by the high energies inherent with plasma. (C. J. Mathai, S. Saravanan, M. R. Anantharaman, S. Venkitachalam, and S. Jayalekshmi, "Characterization of low dielectric constant polyaniline thin film synthesized by ac plasma polymerization technique,"

Journal of Physics D-Applied Physics 35(3), 240-245 (2002); K. Tanaka, K. Yoshizawa, T. Takeuchi, T. Yamabe, and J. Yamauchi, "Plasma Polymerization of Thiophene and 3- Methylthiophene," Synthetic Metals 38(1), 107-116 (1990).; L. M. H. Groenewoud, G. H. M. Engbers, R. White, and J. Feijen, "On the iodine doping process of plasma polymerised thiophene layers," Synthetic Metals 125(3), 429-440 (2001); and L. M. H. Groenewoud, A. E. Weinbeck, G. H. M. Engbers, and J. Feijen, "Effect of dopants on the transparency and stability of the conductivity of plasma polymerised thiophene layers," Synthetic Metals 126(2-3), 143-149 (2002), each of which is incorporated by reference in its entirety.) Another conjugated monomer, 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), can fare much better using PECVD, with reported conductivities as high as 50 S/cm. (M. Murashima, K. Tanaka, and T. Yamabe, "Electrical-Conductivity of Plasma- Polymerized Organic Thin-Films-Influence of Plasma Polymerization Conditions and Surface-Composition," Synthetic Metals 33(3), 373-380 (1989), which is incorporated by reference in its entirety.)

Thermally activated hot-wire CVD can be used to polymerize aniline or vinyl- containing monomers, including phenylenevinylene or vinylcarbazole, but no

conductivities of these materials have been reported. (G. A. Zaharias, H. H. Shi, and S. F. Bent, "Hot Wire Chemical Vapor Deposition as a Novel Synthetic Method for

Electroactive Organic Thin Films," Mat. Res. Soc. Symp. Proc. 814, 112.19.11-112.19.16 (2004); K. M. Vaeth and K. F. Jensen, "Chemical vapor deposition of thin polymer films used is polymer-based light emitting diodes," Advanced Materials 9(6), 490-& (1997); K. M. Vaeth and K. F. Jensen, "Transition metals for selective chemical vapor deposition of parylene-based polymers," Chemistry of Materials 12(5), 1305-1313 (2000); and M. Tamada, H. Omichi, and N. Okui, "Preparation of polyvinylcarbazole thin film with vapor deposition polymerization," Thin Solid Films 268(1-2), 18-21 (1995), each of which is incorporated by reference it its entirety.) Photo-induced CVD can be used to couple thiophene monomers that were halogenated with bromine or chlorine at the 2- and 5-positions. (T. Sorita, H. Fujioka, M. Inoue, and H. Nakajima, "Formation of

Polymerized Thiophene Films by Photochemical Vapor-Deposition," Thin Solid Films 177, 295-303 (1989), which is incorporated by reference in its entirety.) Although the monomers may couple at the halogenated positions, only relatively low conductivities of 10^"13 S/cm can be achieved. However, dibrominated PEDOT can polymerize upon heating and makes films with a conductivity of 20 S/cm. (H. Meng, D. F. Perepichka, M. Bendikov, F. Wudl, G. Z. Pan, W. J. Yu, W. J. Dong, and S. Brown, "Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction," Journal of the American Chemical Society 125(49), 15151-15162 (2003), which is incorporated by reference in its entirety.)

Norborene and a ruthenium(IV)-based catalyst volatilized in a chamber under low pressure can result in a film of polynorborene on a silicon substrate. (H. W. Gu, D. Fu, L. T. Weng, J. Xie, and B. Xu, "Solvent-less polymerization to grow thin films on solid substrates," Advanced Functional Materials 14(5), 492-500 (2004), which is incorporated by reference in its entirety.) The monomer can undergo a ring-opening metathesis polymerization mechanism when contacted by the catalyst. (T. M. Trnka and R. H.

Grubbs, "The development of L2X2Ru=CHR olefin metathesis catalysts: An

organometallic success story," Accounts of Chemical Research 34(1), 18-29 (2001), which is incorporated by reference in it entirety.) The technique can be repeated based on the same polymerization mechanism using 1,3,5,7-cyclooctatetetraene to form polyacetylene. (H. W. Gu, R. K. Zheng, X. X. Zhang, and B. Xu, "Using soft lithography to pattern highly oriented polyacetylene (HOPA) films via solvent- less polymerization," Advanced Materials 16(15), 1356 (2004), which is incorporated by reference in its entirety.) The deposition can be slow and an electrical conductivity was not reported.

Electropolymerization of EDOT has been the most commonly used deposition technique for PEDOT and other conducting polymers. Electrode coatings and freestanding PEDOT films with conductivities around 300 S/cm can be created, which are an order of magnitude higher than the conductivity of polypyrrole films deposited using the same method. Chemical oxidative polymerization of EDOT in a solution containing oxidants like FeCl₃ or Fe(OTs)3 can yield PEDOT material with similar conductivities. The reaction mixture can be cast on a surface leaving a polymerized film as the solvent evaporates and films may also be deposited on substrates that are immersed in the polymerizing reaction mixture. However, like other conjugated polymers that adopt a very rigid conformation in order to maintain electron orbital overlap along the backbone, PEDOT can be insoluble and does not melt, precluding subsequent processing. Bayer circumvented this problem by using a water soluble polyanion, polystyrene sulfonic acid (PSS), during polymerization as the charge -balancing dopant. The aqueous PEDOT: PSS system, now marketed as BAYTRON P™, has a good shelf life and film forming capabilities while maintaining its transparency, stability, and a conductivity of 10 S/cm. However, the PSS dopant can incorporate a non-conducting matrix material and can make the coating solution acidic. This fact can lead to different film forming characteristics depending on the ability of the solution to wet different materials like glass, plastic, or other active layers in a device. In addition, some devices simply cannot be compatible with wet processing techniques.

Therefore, the development of a robust vapor-deposition technique for PEDOT films could simplify the coating process on a variety of organic and inorganic materials since it would not depend on evenly wetting the substrate surface. Vapor-phase deposition could also provide uniform coatings on substrates with high surface areas due to roughness or fibrous and porous morphologies. Increasing the effective surface area of devices can improve operating efficiencies and coating unconventional surfaces like paper, fabric, or small particles can lead to the innovation of new devices. Vapor-phase techniques using oxidant-enriched substrates which have been coated with solutions of Fe(III) tosylate and allowed to dry have been developed. Exposing the treated surface to EDOT vapors can result in the polymerization of films with conductivities reported to be as high as 1000 S/cm. (J. Kim, E. Kim, Y. Won, H. Lee, K. Suh, Synthetic Metals 139, 485 (2003); and B. Winther- Jensen, K. West, Macromolecules 37, 4538 (2004), each of which is incorporated by reference in its entirety.)

A method of making a conducting material can be a chemical vapor deposition (CVD) process that forms thin films of electrically active polymers. (See, for example, U.S. Patent 7,618,680 and references cited therein, each of which is incorporated by reference in its entirety.) In one embodiment, the technique can make PEDOT that has a conductivity over 4 S/cm and can be spectroscopically comparable to commercial product deposited from the solution phase. This technique can be applicable to other oxidatively polymerized conducting materials like polypyrrole, polyaniline, polythiophene, or their substituted derivatives. Side reactions stemming from acid generation during oxidative polymerization can lead to bond breakage in the monomer and the formation of unconjugated oligomers that can result in films with low conductivities. These unwanted reactions can be minimized via three different methods: introducing pyridine as a base, heating the substrate (e.g., the surface to be coated), and applying a bias to the sample stage.

CVD can be an all-dry process for depositing thin films of conducting polymers that are currently available on the market only as solution-based materials. Commercial PEDOT films deposited onto anodes from solution can facilitate hole injection and can result in significant efficiency gains on the order of 50% for organic LED and

photovoltaic devices. Using CVD to provide uniform coatings on rough electrode surfaces can lead to further improvements in efficiency by increasing the effective surface area while avoiding sharp electrode features from protruding through the film and shorting the device. The absence of the acidity associated with solution-based films can reduce corrosion of neighboring layers that can cause early device failure. Moderate stage temperatures and vapor phase coating can allow depositing conducting films on a wide range of unconventional organic and inorganic high surface-area materials, including paper, fabric, and small particles. CVD can be a significant tool for organic

semiconductor manufacturers seeking capabilities to incorporate conducting polymers in all-dry fabrication processes.

Polymerization of EDOT.

The oxidation of 3,4-ethylenedioxythiophene (EDOT) to form PEDOT can be analogous to the oxidative polymerization of pyrrole, which has been described with a mechanism proposed by Diaz. (S. Sadki, P. Schottland, N. Brodie, G. Sabouraud, Chemical Society Reviews 29, 283 (2000); and E. M. Genies, G. Bidan, A. F. Diaz,

Journal of Electroanalytical Chemistry 149, 101 (1983), each of which is incorporated by reference in its entirety.) The first step can be the oxidation of EDOT, which generates a radical cation that has several resonance forms. The combination of two of these radicals and subsequent deprotonation can form a neutral dimer. Substitution of the EDOT thiophene ring at the 3,4-positions can block β-coupling, allowing new bonds only at the 2,5-positions. The alternating single and double bonds of the dimer can give π- conjugated or delocalized electrons, making it easier to remove an electron from the dimer relative to the monomer. In other words, the dimer can have a lower oxidation potential than the monomer. The dimer can be oxidized to form another positively charged radical that can undergo coupling and deprotonation with other monomeric or oligomeric cations. Eventually, chains of neutral PEDOT with alternating single and double bonds can be formed.

The neutral PEDOT polymer can be further oxidized to create a positive charge along the backbone every three or four chain segments. A "dopant" anion can ionically bind to the polymer and balance the charge. The oxidized form of PEDOT can be a conducting form of the polymer. Neutral PEDOT can have a dark blue/purple color and the doped form can be very light blue.

The acidic strength of the reaction environment can be one aspect of the mechanism to be considered, because it can have a number of effects on the

polymerization conditions, including the oxidation potential of the oxidant, which can be decreased with the addition of a base. Some acidification of the reaction mixture can speed the rate of polymerization through an acid-initiated coupling mechanism, which can contribute to additional chain growth. One caveat of acid-initiated coupling can be that the resulting polymer is not conjugated and may not be electrically conducting without subsequent oxidation. If the acidic strength is too high, it can be possible to saturate the 3,4-positions of a reacting EDOT radical, resulting in a trimer with broken conjugation, quenching electrical conductivity. (T. F. Otero, J. Rodriguez, Electrochimica Acta 39, 245 (1994), which is incorporated by reference in its entirety).

Evidence has also been presented that very acidic conditions can break the dioxy bridge on the EDOT ring leading to imperfections that reduce conductivity. (B. Winther- Jensen, K. West, Macromolecules 37, 4538 (2004), which is incorporated by reference in its entirety). Adding pyridine as a base to the system to achieve an acidic strength strong enough to maintain the oxidation potential of the oxidant, but not strong enough to cause bond cleavage of the monomer, can yield PEDOT films with conductivities reported to be as high as 1000 S/cm. Oxidative Chemical Vapor Deposition (oCVD).

oCVD of conducting polymers can be a substrate-independent, one-step, solvent- free, and conformal process in which polymerized thin films form on the substrate by simultaneous exposure to vapor-phase monomer and oxidant reactants at low substrate temperatures (20- 100 °C), moderate vacuum (-0.1 Torr), and at rates that can exceed 10 ran min^"1 (Fig. 10a) (see, e.g., M. E. Alf et al, Adv. Mater. 22, 1993 (2010); and S. H. Baxamusa, S. G. Im, K. K. Gleason, Phys Chem Chem Phys 11, 5227 (2009), each of which is incorporated by reference in its entirety). oCVD allows direct control of thickness, dopant concentration, work function, and conductivity and is compatible with substrates that are susceptible to solvent and processing damage.

oCVD can generally take place in a reactor. Precursor molecules, consisting of a chemical oxidant and a monomer species, can be fed into the reactor. The oxidant can be a metal-containing oxidant. This process can take place at a range of pressures from atmospheric pressure to low vacuum. In certain embodiments, the pressure can be about 760 Torr; in other embodiments, the pressure can be about 300 Torr; in other

embodiments, the pressure can be about 30 Torr; in other embodiments, the pressure can be about 3000 mTorr; in yet other embodiments, the pressure can be about 300 mTorr. Chemical oxidant species can be extremely heavy, but can be sublimed onto a substrate surface using a carrier gas and a heated, porous crucible installed inside the reactor directly above the sample stage. The oxidant source can also be installed on the exterior of the vacuum chamber. Evaporation of the oxidant can also take place in a resistively heated container inside the reaction chamber. In certain embodiments, evaporation of the oxidant can take place in a resistively heated container inside the reaction chamber. The oxidant can be underneath the substrate surface to be coated. The monomer species can be provided to the substrate surface, which may have been previously exposed to the oxidant. The monomer species can be provided to the reactor, for example, in vapor form. In certain embodiments, the monomer species can be delivered from a source external to the reactor. The oxidant can form a thin, conformational layer on the substrate surface. The conformational layer can react with monomer molecules as they adsorb. An acid- catalyzed side reaction can lead to broken monomer bonds and non-conjugated oligomers can inhibit the formation of conjugated, electrically active polymer. These side reactions may be reduced using one or more the following techniques: introducing a base, such as pyridine, to react with any acid that is formed in situ; heating the substrate to

temperatures above about 60 °C, 70 °C, 80 °C or 90 °C, for example, to accelerate evaporation of the acid as it is formed; and biasing the substrate with a positive charge using a DC power supply to favor the oxidation of monomeric and oligomeric species adsorbed on the substrate. Biasing can also provide directionality to charged oligomers during polymer chain growth. The ordering of the polymer chains that results can contribute to higher electrical conductivities.

The deposited film then can be heated, sometimes under vacuum (e.g., -15 mmHg, -30 mmHg, or -45 mmHg), to remove unreacted monomer. Rinsing the dried film in a solvent, for example, methanol or water, can remove reacted metal-containing oxidant from the film, in some cases can change the color from hazy yellow to a clear sky blue hue. Rinsing the dried film in a solution of "dopant" ionic salts, such as NOPF₆ in acetonitrile, can promote the oxidized form of the conducting polymer by balancing positive charges that are induced along the polymer chain with anions from the salt.

Methods of Making a Conducting Material.

A method of making a conducting material can include providing a substrate. The substrate can have a surface area greater than area the substrate occupies. The substrate can have a surface area that is greater than 1.5 times, greater than 2 times, greater than 5 times, greater than 10 times, greater than 25 times, greater than 50 times, greater than 100 times, or greater than 500 times the area the substrate occupies.

In certain embodiments, the substrate can have a texture. For example, the texture can be fibrous, porous, granulated, patterned, ridged, stippled, corrugated, perforated, milled, or brushed. The substrate can include more than one texture, or a texture can be present on only a portion of the substrate. The substrate can be flexible.

The substrate can be a fibrous substrate, for example, paper or fabric. A fibrous substrate can include fibers, threads or filaments. Paper can be a felted sheet of fibers deposited on a screen from a water suspension. Examples of paper can include rice paper, tracing paper, tissue paper, toilet paper, bathroom tissue, facial tissue, newspaper, wax paper, paper currency, banana paper, inkjet paper, wallpaper, sandpaper, cotton paper, construction paper, book paper, printer paper, parchment, fish paper, TYVEK™, wove paper, buckypaper, and paper towels. Paper can be made from a number of materials including plant fibers, for example, fibers from wood, cotton, rice, wheat, bark, bamboo, hemp, or papyrus. Paper can also be made from materials including carbon, graphene oxide, or plastic. Products of any of these materials, or combinations of any of these materials can also be used to form paper.

Fabric can be a material made by weaving, felting or knitting natural or synthetic fibers or filaments. A fabric can be made from natural sources, which can include for example, from carbon, cotton, silk, fleece, fur, leather, angora, mohair, alpaca wool, satin, goat wool, horse hair, flax, camel hair, cashmere, vicuna fleece, llama wool, milk proteins, grass, hemp, rush, straw, bamboo or wood. The fabrics made from natural sources can include linen, taffeta, tweed, wool, silk, canvas, cheesecloth, gauze, corduroy, denim, moleskin, poplin, sacking, terry cloth, lyocell, or velvet. Minerals, such as asbestos or basalt, can be used to make fabrics. Fabrics can be made from glass or metals, such as gold, silver, titanium, aluminum, copper or steel. A fabric can be synthetic, for example, satin, rayon, acrylic, acetate, nylon, aramid, latex, polyester, spandex, chiffon, polyvinyl chloride, sateen, olefin, ingeo, lurex, tulle, or viscose. A fabric can be a blend of natural materials, synthetic materials, or both.

The substrate can also be porous, meaning it can include pores or holes. A porous material can include, for example, plastic, sponge, ceramic, wood, clay, carbon or silicon. The substrate can be transparent or semi-transparent. The substrate can allow greater than 90%, greater than 80%, greater than 70%, greater than 60%, greater than 50% or greater than 25% of light that contacts the substrate to pass through the substrate.

The light passing through the substrate can be light within the solar spectrum. The light can include electromagnetic radiation with wavelengths falling in the visible spectrum, the ultraviolet spectrum and the infrared spectrum. More specifically, the light can include electromagnetic radiation with a wavelength of 100 to 280 nm, 280 to 315 nm, 315 to 400 nm, 400 to 700 nm, 700 nm to 1 μιη, 1 μιη to 2 μιη, or 2 μιη to 3 μιη. The light can include electromagnetic radiation classified as ultraviolet C, ultraviolet B, ultraviolet A, visible, infrared A, infrared B or infrared C.

The substrate can be free from pre-treatments. The substrate can also be free from solvents or wetting agents. The substrate can be hydrophobic or hydrophilic.

The substrate can be fragile, for example, it can be easily folded, shaped, torn or cut. The substrate can also be easily damaged by common processing agents such as solvents, plasmas or heat. The substrate can be flexible, e.g., easily bent, folded or creased. A flexible substrate can be brittle or non-brittle. The substrate can be stretchable.

The method of making a conducting material can include coating at least a portion of a surface of the substrate with a conductive polymer. Coating at least a portion of the substrate with a conductive polymer can include oxidative chemical vapor deposition, which can take place in a reactor or a reaction chamber. Coating at least a portion of a surface of the substrate with a conductive polymer can include contacting the substrate with an oxidant. The oxidant can be gaseous. The oxidant can be vaporized to form a gaseous oxidant. Vaporizing can include sublimation using a carrier gas and a heated, porous crucible installed inside the reactor directly above the sample stage where the substrate can be placed. Vaporization can also take place in a resistively heated container inside the reaction chamber underneath the substrate surface.

The oxidant can also be a metal-containing oxidant, for example, iron(III) chloride, iron(III) toslyate, potassium iodate, potassium chromate, ammonium sulfate or tetrabutylammonium persulfate. The oxidant can have an oxidation potential between about 0.5 V and about 1.0 V, more specifically, about 0.75 V. The entire surface can be contacted with the oxidant or a portion of the surface can be contacted. Contacting the substrate with the oxidant can form an oxidant-enriched portion of the substrate. The portion of the substrate can be a portion of the surface.

The method of making a conducting material can include heating the oxidant enriched portion of the substrate. Heating the oxidant enriched portion of the substrate can accelerate evaporation of acid that may be formed on the substrate. The substrate can be heated by heating a stage on which the substrate is placed, heating the reaction chamber or other methods known to those of skill in art for heating a substrate.

Acid-catalyzed side reactions during oCVD can lead to broken monomer bonds and/or non-conjugated oligomers, which can inhibit the formation of conjugated, electrically active polymer. However, these side reactions may be reduced using one or more the following techniques: introducing a base, such as pyridine, to react with any acid that is formed in situ; heating the substrate to temperatures above about 60 °C, 70 °C, 80 °C or 90 °C, for example, to accelerate evaporation of the acid as it is formed; and biasing the substrate with a positive charge using a DC power supply to favor the oxidation of monomeric and oligomeric species adsorbed on the substrate. Biasing also provided directionality to charged oligomers during polymer chain growth. The ordering of the polymer chains that results may contribute to higher electrical conductivities.

The method of making a conducting material can include contacting the oxidant enriched surface with a base. The base can be a gaseous base. The base can be an optionally substituted pyridine.

The method of making a conducting material can include contacting the oxidant enriched portion of the substrate with a monomer. The monomer may be gaseous. The monomer can be vaporized to form a gaseous monomer. Vaporizing can include sublimation. The monomer can be vaporized inside the reaction chamber or gaseous monomer can be provided from a source external to the reaction chamber. The monomer can be an optionally substituted thiophene, optionally substituted pyrrole, optionally substituted anilines, phenanthrolines, furans, heteroarenes including more than one ring heteroatom, benzenoid arenes, non-benzenoid aromatic compounds, or combinations thereof. The monomer can be 3,4 ethylenedioxy thiophene. Contacting the oxidant- enriched surface with the monomer can result in polymerization of the monomer and the formation of a polymer coated surface.

In certain embodiments, the deposited film then may be heated, sometimes under vacuum (e.g., 15 mmHg, 30 mmHg, or 45 mmHg), to remove unreacted monomer. Following polymerization, the polymer coated surface can be washed with a solvent, which can be, for example, water, methanol, ethanol, isopropanol, acetonitrile or mixtures thereof. In some cases, this changes the color from hazy yellow to a clear sky blue hue.

A gaseous precursor, such as an epoxide, can be thermally activated to provide an initiator for the oxidative polymerization of the conductive polymer. The precursor can be thermally activated with the use of a hot filament. The polymer coating can include bicyclic thiophene, for example, a heterobicyclic thiophene such as poly(3,4- ethylenedioxy thiophene) .

The method of making a conducting material can include contacting the conductive polymer coated substrate with a dopant, most commonly a dopant anion. A dopant can contribute to the conductivity of the polymer coating. A dopant anion can provide stability enhancement for electroactive polymers. The dopant may be any compound as long as it has a doping ability (i.e. stabilizing ability). For example, an organic sulfonic acid, an inorganic sulfonic acid, an organic carboxylic acid or salts thereof such as a metal salt or an ammonium salt may be used. More specifically, it can include chloride, bromide, iodide, fluoride, phosphate, sulfonate or nitrosonium hexafluorophosphate. The dopant can be added to the oxidizing agent and/or the monomer, can be allowed to be present together at the time of polymerization or can be added by other methods known to those of skill in the art. In certain embodiments the dopant molecule comprises aqueous solutions of the acids selected from the group consisting of phosphoric acid, triflic acid, hydrochloric acid, methanesulfonic acid, oxalic acid, pyruvic acid, or acrylic acid, or a poly anion incorporating one or more of the aforementioned types of acids. In certain embodiments, rinsing the dried film in a solution of "dopant" ionic salts, such as NOPF₆ in acetonitrile, can promote the oxidized form of a conducting polymer by balancing positive charges that are induced along the polymer chain with anions from the salt.

Once the conductive polymer is formed, the conductive polymer coated surface can be heated under vacuum to dry. The surface can be heated using a heated stage, heating the reaction chamber, or heated by other methods known to those of skill in the art.

Substrates can have textured surfaces that require fabrication processes capable of conformally coating complex geometries. The conductive polymer can be conformal to the substrate. For example, the polymer can form a layer directly around the fibers of the substrate (Fig. 7f), can form a layer directly in holes of a porous or perforated substrate (not shown), or can form a layer directly over granulated, ridged, patterned, stippled, corrugated, milled, or brushed substrates (not shown). This allows the conductive polymer to get into the "nooks and crannies" of the substrate. The conductive polymer coating can have essentially the same shape and contours of the substrate, for example, forming a sleeve on the fibers. This is in contrast to conductive polymers deposited on substrates by techniques other than oCVD, where the conductive polymer can blanket the substrate (Fig. 7e) or can have irregular dimensions along the texture of the substrate and demonstrate poor morphology (Fig. 7d).

The conductive polymer can directly conform to the substrate. Pre-treatment steps or protective layers may not be required for the conductive polymer to adhere to the substrate. Pre-treatment steps can include exposing the substrate to solvents or wetting agents. The conductive polymer can have a high degree of adhesion to the substrate. The high degree of adhesion can result from in situ covalent bonding, or chemical grafting, of the polymer to a substrate possessing functional groups upon film formation. Functional groups can be present on polystyrenes or polyethylene terephthalates, for example. The high degree of adhesion can be advantageous for roll-to-roll processing and for flexible and stretchable electronics, where mechanical stresses could otherwise result in cracking or delamination.

The conductive polymer coating can be of a uniform thickness (i.e., said thickness does not vary more than 10% over the surface of the article; or by more than 5% over the surface of the article; or by more than 1% over the surface of the article). The thickness of the polymer coating can be between 0 and 100 nm, for example, between 0 and 10 nm, between 10 and 20 nm, between 20 and 30 nm, between 30 and 40 nm, between 40 and 50 nm, between 50 and 75 nm, between 75 and 100 nm. The thickness of the polymer coating can be greater than 100 nm. More specifically, the thickness of the polymer coating can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 75 nm, 80 nm, 90 nm or 100 nm.

The conductive polymer coating can have a mass per surface area of less than about 500 μg/cm², less than about 100 μg/cm², less than about 50 μg/cm², less than about 10 μg/cm², or less than about 5 μg/cm². The required mass per surface area depends on the specific surface area of the substrate to be coated. A smooth flat substrate, 1 cm² in area can require coverage of only 1 cm² of area and thus the specific surface area of 1 cm² /cm². However, a 1 cm² section of fabric can have a specific surface area greater than 1 because each surface-accessible fiber of the fabric must be coated. The gaseous reactants of the inventive processes can penetrate into the fabric and coat these internal surfaces. The specific surface area can depend on the packing density of the fibers and total thickness of the fabric. The thickness (cm) of the coating multiplied by the specific surface area (cm²/cm²) of the fabric and the density of the coating (g/cm³) will yield the mass per surface area (g/cm²).

The methods of making a conducting material can have several advantages. In addition to achieving polymerization from vapor-phase reactants and conformal thin- film formation in a single step, the method can impart excellent substrate adhesion through in situ covalent bonding (chemical grafting) and can allow direct control over thickness, dopant concentration, work function, and conductivity. (Im, S. G., Yoo, P. J., Hammond, P. T., Gleason, K. K., Grafted conducting polymer films for nano-patterning onto various organic and inorganic substrates by oxidative chemical vapor deposition. Adv. Mater. 19, 2863 (2007); Im, S. G., Gleason, K. K., Systematic control of the electrical conductivity of poly(3,4-ethylenedioxythiophene) via oxidative chemical vapor deposition.

Macromolecules 40, 6552 (2007); and Im, S. G., Gleason, K. K., Olivetti, E. A., Doping level and work function control in oxidative chemical vapor deposited poly (3,4- ethylenedioxythiophene). Appl. Phys. Lett. 90 (2007), each of which is incorporated by reference in its entirety). Films can form at low substrate temperatures (20-100 °C), moderate vacuum (-0.1 Torr), and at rates that can exceed 10 nm min^"1. Moreover, since there are no solubility requirements, the polymer coated substrates may not be bound by the molecular weight and dopant restrictions that can limit conductivity in solution-cast polymers. (Ha, Y. H. et al., Towards a transparent, highly conductive poly(3,4- ethylenedioxythiophene). Adv. Funct. Mater. 14, 615 (2004), which is incorporated by reference in its entirety). Finally, the method can be achieved by all dry processing.

Conducting polymers can be fabricated directly on ultra- lightweight "everyday" substrates, including as-purchased fiber-based papers (-0.001 g cm^"2, ~40-μιη thick), without any pretreatment steps or protecting layers. Photovoltaics formed using this technique can demonstrate power-to-weight ratios over 500 W kg^"1. The highly conductive polymer electrodes (100-1000 S cm^"1) can be simultaneously synthesized and deposited without solvents as conformal, transparent thin films at low temperature via oxidative chemical vapor deposition (oCVD). The polymer electrodes can retain their electrical integrity even after severe deformation: >1000 flexing cycles at <5 mm radius, >100 creasing cycles, and stretching to -200%. The polymer electrodes can exhibit comparable performance to conventional ITO-based devices, can be flexed >100 times while maintaining nearly 100% of their starting efficiencies, and can retain power generation in air when folded into large-area three-dimensional structures.

The substrate independence of oCVD was demonstrated by depositing poly (3 ,4- ethylenedioxythiophene) (PEDOT) conductive thin films (100-1000 S-cni ¹ ) on Saran™ wrap (hydrophobic, ~ 10-μι» thick), bathroom tissue (porous/absorbent), and rice paper (water soluble) with no pre- or post-treatment and at identical conditions (described in further detail below). Because of their respective properties, such substrates are difficult to coat by other solvent-based methods. For example, the solution-cast conducting polymer CLEVIOS™ PH 750 (>650 S cm^"1 as a dried film) does not controllably wet these substrates and can easily damage them via capillary forces or dissolution. Similarly, other vapor-phase polymerization (VPP) techniques for conducting polymers rely on solvent casting of oxidants, which can easily degrade such delicate substrates. See, for example, B. Winther-Jensen, K. West, Macromolecules 37, 4538 (2004); and S.

Admassie et ah , Sol. Energy Mater. Sol. Cells 90, 133 (2006), each of which is incorporated by reference in its entirety. By using vapor-only delivery of both monomer and oxidant, it is possible to simply and non-destructively vapor-pattern oCVD polymer electrodes in situ. In particular, patterning can be achieved via shadow masking and maintaining the partial pressure of one of the reactive species sufficiently close to its saturation pressure at the substrate. Doing so thereby prevents significant mask undercutting and creating well-defined polymer patterns on any surface of choice (Figs. 10b and 14). Thin layers of conducting polymers can be patterned over large areas.

Conducting Material.

A conducting material can include a substrate and a conductive polymer coating on a surface of the substrate (Fig. 9a).

The substrate can have a surface area greater than area the substrate occupies.

The substrate can have a surface area that is greater than 1.5 times, greater than 2 times, greater than 5 times, greater than 10 times, greater than 25 times, greater than 50 times, greater than 100 times, or greater than 500 times the area the substrate occupies. The substrate can have a texture. For example, the texture can be fibrous, porous, granulated, patterned, ridged, stippled, corrugated, perforated, milled or brushed. The substrate can include more than one texture, or a texture can be present on only a portion of the substrate. The substrate can be flexible.

The substrate can be a fibrous substrate, for example, paper or fabric. A fibrous substrate can include fibers, threads or filaments. Paper can be a felted sheet of fibers deposited on a screen from a water suspension. Examples of paper can include rice paper, tracing paper, tissue paper, toilet paper, bathroom tissue, facial tissue, newspaper, wax paper, paper currency, banana paper, inkjet paper, wallpaper, sandpaper, cotton paper, construction paper, book paper, printer paper, parchment, fish paper, TYVEK™, wove paper, buckypaper, or paper towels. Paper can be made from a number of materials including plant fibers, for example, fibers from wood, cotton, rice, wheat, bark, bamboo, hemp, or papyrus. Paper can also be made from materials including carbon, graphene oxide, or plastic. Products of any of these materials, or combinations of any of these materials can also be used to form paper.

The substrate can also be porous, meaning it can include pores or holes. A porous material can include, for example, plastic, sponge, ceramic, wood, clay, carbon or silicon.

The substrate can be transparent or semi-transparent. The substrate can allow greater than 90%, greater than 80%, greater than 70%, greater than 60%, greater than 50% or greater than 25% of light that contacts the substrate to pass through the substrate. The light passing through the substrate can be light within the solar spectrum. The light can include electromagnetic radiation with wavelengths falling in the visible spectrum, the ultraviolet spectrum and the infrared spectrum. More specifically, the light can include electromagnetic radiation with a wavelength of 100 to 280 nm, 280 to 315 nm, 315 to 400 nm, 400 to 700 nm, 700 nm to 1 μιη, 1 μιη to 2 μιη, or 2 μιη to 3 μιη. The light can include electromagnetic radiation classified as ultraviolet C, ultraviolet B, ultraviolet A, visible, infrared A, infrared B or infrared C.

The substrate can be fragile, for example, it can be easily folded, shaped, torn, or cut. The substrate can also be easily damaged by common processing agents such as solvents, plasmas or heat. The substrate can be flexible, e.g., easily bent, folded or creased. A flexible substrate can be brittle or non-brittle. The substrate can be stretchable.

The conductive polymer can include monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles, optionally substituted anilines, phenanthrolines, furans, heteroarenes including more than one ring heteroatom, benzenoid arenes, non-benzenoid aromatic compounds, or combinations thereof. The polymer coating can include bicyclic thiophene, for example, a heterobicyclic thiophene such as poly(3,4-ethylenedioxythiophene). Poly(3,4-ethylenedioxythiophene) can be made up of monomeric units derived from 3,4 ethylenedioxythiophene.

The conductive polymer can be a p-type semiconductor and have an excess of holes (i.e. spaces that accept electrons). The conductive polymer can be an n-type semiconductor and have an excess of free electrons.

The conductive polymer can directly conform to the substrate. Pre-treatment steps or protective layers may not be required for the conductive polymer to adhere to the substrate. Pre-treatment steps can include exposing the substrate to solvents or wetting agents. The conductive polymer can have a high degree of adhesion to the substrate. The high degree of adhesion can result from in situ covalent bonding, or chemical grafting, of the polymer to a substrate possessing functional groups upon film formation. The high degree of adhesion can be advantageous for roll-to-roll processing and for flexible and stretchable electronics, where mechanical stresses could otherwise result in cracking or delamination.

The conductive polymer coating can be of a uniform thickness (i.e., said thickness does not vary more than 10% over the surface of the article; or by more than 5% over the surface of the article; or by more than 1% over the surface of the article). The thickness of the polymer coating can be between 0 and 10 nm, between 10 and 20 nm, between 20 and 30 nm, between 30 and 40 nm, between 40 and 50 nm, between 50 and 75 nm, between 75 and 100 nm or greater than 100 nm. More specifically, the thickness of the polymer coating can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 75 nm, 80 nm, 90 nm or 100 nm.

The conductive polymer coating can have a mass per surface area of less than about 500 μg/cm², less than about 100 μg/cm², less than about 50 μg/cm², less than about 10 μg/cm², or less than about 5 μg/cm². The required mass per surface area depends on the specific surface area of the substrate to be coated. A smooth flat substrate, 1 cm² in area can require coverage of only 1 cm² of area and thus the specific surface area of 1 cm² /cm². However, a 1 cm² section of fabric can have a specific surface area greater than 1 because each surface-accessible fiber of the fabric must be coated. The gaseous reactants of the inventive processes can penetrate into the fabric and coat these internal surfaces. The specific surface area can depend on the packing density of the fibers and total thickness of the fabric. The thickness (cm) of the coating multiplied by the specific surface area (cm²/cm²) of the fabric and the density of the coating (g/cm³) will yield the mass per surface area (g/cm²). The conductive polymer coating can also include a dopant, most commonly a dopant anion. A dopant can contribute to the conductivity of the polymer coating. A dopant anion can provide stability enhancement for electroactive polymers. The dopant may be any compound as long as it has a doping ability (i.e. charge stabilizing ability). For example, an organic sulfonic acid, an inorganic sulfonic acid, an organic carboxylic acid or salts thereof such as a metal salt or an ammonium salt may be used. More specifically, it can include chloride, bromide, iodide, fluoride, phosphate, sulfonate or nitrosonium hexafluorophosphate. In certain embodiments the dopant molecule comprises aqueous solutions of the acids selected from the group consisting of phosphoric acid, triflic acid, hydrochloric acid, methanesulfonic acid, oxalic acid, pyruvic acid, and acrylic acid, or a poly anion incorporating one or more of the aforementioned types of acids.

The conducting material can withstand deformation including repeated folding, stretching, bending, arching, rolling, or perforations. The conducting material can withstand severe deformation, including greater than 1000 flexing cycles (less than 5 mm radius), greater than 100 creasing cycles, or stretching greater than 150%. In contrast, flexing of commercially fabricated ITO-coated PET substrates decreased the film conductance over 400-fold due to formation of cracks (Fig. 15). As described in further detail below, oCVD PEDOT on 10-μιη thick Saran™ wrap increased in conductivity under moderate stretching (25%) and maintained significant electrical conductance until substrate failure (~ 200% extension). This far exceeded the stretchability of metals, metal oxides, graphene, and even "wavy" silicon ribbons (electrical failure at -5-30% extension) (see, e.g., D. R. Cairns et αί , ΑρρΙ. Phys. Lett. 76, 1425 (2000); T. Li, et al , Appl. Phys. Lett. 85, 3435 (2004); K. S. Kim et al , Nature 457, 706 (2009); and J. A. Rogers, T. Someya, Y. G. Huang, Science 327, 1603; each of which is incorporated by reference in its entirety). This stretchability was comparable to some of the best reports for conducting polymer films and composites (electrical failure at -100-200% extension) (see, e.g., T. S. Hansen, et al, Adv. Funct. Mater. 17, 3069 (2007); T. Sekitani et al., Science 321, 1468 (2008); and M. G. Urdaneta, R. Delille, E. Smela, Adv. Mater. 19, 2629 (2007); each of which is incorporated by reference in its entirety). Finally, oCVD PEDOT on fiber-based paper retained significant conductance after over 100 folding iterations (to a crease). Evaporated metal films, in contrast, exhibit complete electrical failure after fewer than 10 folding iterations (A. C. Siegel et al. , Adv. Funct. Mater. 20, 28 (2010), which is incorporated by reference in its entirety).

How well a conductive material withstands deformation can be determined by observing the presence or absence of physical damage to the conducting material, for example, cracks, tears, ruptures, snags, pills, unravels, pleats, creases, or changes in color, shape or thickness. Withstanding the deformation can be determined by measuring properties of the conducting material such as current density- voltage characteristics, work function, tensility or temperature.

A method of testing the conducting material can include making the conducting material and comparing it to a control device. The control device can have the structure ITO/PEDOT:PSS/CuPc/C₆₀/BCP/Ag. In particular, it can have the structure ITO (100 nm)/PEDOT:PSS (70 nm)/CuPc (20 nm)/C₆₀ (40 nm)/BCP (12nm)/Ag (1000 nm). A control electrode can be the ITO/oCVD PEDOT electrode. A method of testing the conducting material can also include measuring the current density-voltage characteristics.

The conducting material can perform comparably with conventional anode structures and exhibit improved open-circuit voltage relative to bare ITO. The

conducting material can provide advantageous work function and morphological benefits. The conducting material can be more conductive than a control electrode, for example, order of magnitude or more conductive than a PEDOT:PSS buffer layer. A higher fill factor can be exhibited by the conducting material when compared to the control electrode.

Light Absorbing or Light Emitting Device.

A light absorbing or a light emitting device can include a substrate and a conductive polymer coating on a surface of the substrate. The substrate with a conductive polymer coating on a surface of the substrate can be a conducting material. The conducting material can be part of a light absorbing device, for example, a photovoltaic. The conducting material can be part of a light emitting device, for example, a light emitting diode.

The substrate can have a surface area greater than area the substrate occupies. The substrate can have a surface area that is greater than 1.5 times, greater than 2 times, greater than 5 times, greater than 10 times, greater than 25 times, greater than 50 times, greater than 100 times, or greater than 500 times the area the substrate occupies. The substrate can have a texture. For example, the texture can be fibrous, porous, granulated, patterned, ridged, stippled, corrugated, perforated, milled or brushed. The substrate can include more than one texture, or a texture can be present on only a portion of the substrate. The substrate can be flexible.

In certain embodiments, the substrate can be a plastic, for example, polystyrene, polyamide, polyvinyl chloride, polyethylene, acrylonitrile butadiene styrene, polyester, polyurethane, polypropylene, polycarbonate, polyvinylidene chloride, polymethyl methacrylate, polytetrafluoroethlyene, polyetheretherketone, polyetherimide, phenolic, urea-formaldehyde, melamine formaldehyde, polylactic acid, plastarch, polyethylene terephthalate or combination thereof. The substrate can also be an elastomer such as polydimethylsiloxane, latex or rubber. The plastic can be solid or textured.

A surface of the substrate can include a plurality of functional groups. A functional group can include a hydroxide, an alkane, an aliphatic ring, an alkene, a benzenoid ring, a thiol, an oxime, a thiocyanate, a cyanamide, a sulfonic acid, a phosphinic acid, a thiophosphate acid, an aldehyde, a ketone, an alkyne, a carboxylic acid, a carbonyl, an ester, an ether, an amide, an amine, a halide, a phenol or a nitrile.

Functional groups can include an aromatic functional group such as an aromatic ester, an aromatic amide, an aromatic nitro, a phenol, a benzenoid, a benzene, an aromatic ester or an aromatic carboxylic acid. The polymer can interact, e.g. bond, with the functional groups on the substrate. A bond can be a covalent, ionic, van der Waals, dipolar or hydrogen bond.

The substrate can be transparent or semi-transparent. The substrate can allow greater than 90%, greater than 80%, greater than 70%, greater than 60%, greater than

50% or greater than 25% of light that contacts the substrate to pass through the substrate.

The light passing through the substrate can be light within the solar spectrum. The light can include electromagnetic radiation with wavelengths falling in the visible spectrum, the ultraviolet spectrum or the infrared spectrum. More specifically, the light can include electromagnetic radiation with a wavelength of 100 to 280 nm, 280 to 315 nm, 315 to 400 nm, 400 to 700 nm, 700 nm to 1 μιη, 1 μιη to 2 μιη, or 2 μιη to 3 μιη. The light can include electromagnetic radiation classified as ultraviolet C, ultraviolet B, ultraviolet A, visible, infrared A, infrared B or infrared C.

The conductive polymer can include monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles, optionally substituted anilines, phenanthrolines, furans, heteroarenes including more than one ring heteroatom, benzenoid arenes, non-benzenoid aromatic compounds, or combinations thereof. The polymer coating can include bicyclic thiophene, for example, a heterobicyclic thiophene such as poly(3,4-ethylenedioxythiophene). Poly(3,4-ethylenedioxythiophene can be made up of monomeric units derived from 3,4 ethylenedioxythiophene.

The conductive polymer can directly conform to the substrate. Pre-treatment steps or protective layers may not required for the conductive polymer to adhere to the substrate. Pre-treatment steps can include exposing the substrate to solvents or wetting agents. The conductive polymer can have a high degree of adhesion to the substrate. The high degree of adhesion can result from in situ covalent bonding, or chemical grafting, of the polymer to a substrate possessing functional groups upon film formation. The high degree of adhesion can be advantageous for roll-to-roll processing and for flexible and stretchable electronics, where mechanical stresses could otherwise result in cracking or delamination.

The conductive polymer coating can also include a dopant, most commonly a dopant anion. A dopant can contribute to the conductivity of the polymer coating. A dopant anion can provide stability enhancement for electroactive polymers. The dopant may be any compound as long as it has a doping ability (i.e. charge stabilizing ability). For example, an organic sulfonic acid, an inorganic sulfonic acid, an organic carboxylic acid or salts thereof such as a metal salt or an ammonium salt may be used. More specifically, it can include chloride, bromide, iodide, fluoride, phosphate, sulfonate or nitrosonium hexafluorophosphate. In certain embodiments the dopant molecule comprises aqueous solutions of the acids selected from the group consisting of phosphoric acid, triflic acid, hydrochloric acid, methanesulfonic acid, oxalic acid, pyruvic acid, and acrylic acid, or a poly anion incorporating one or more of the aforementioned types of acids.

The conducting material can withstand deformation, including repeated, folding, stretching, bending, arching, rolling, or perforations. The conducting material can withstand severe deformation, including greater than 1000 flexing cycles (less than 5 mm radius), greater than 100 creasing cycles, and stretching greater than 150%. Withstanding the deformation can be determined by observing the presence or absence of physical damage to the conducting material, for example, cracks, tears, ruptures, snags, pills, unravels, pleats, creases, or changes in color, shape or thickness. Withstanding the deformation can be determined by measuring properties of the conducting material such as current density-voltage characteristics, work function, tensility, or temperature.

A light absorbing or light emitting device can include an electrode and an energy converting region (Fig. 9b). The energy converting region can be between the conductive polymer and the electrode.

The electrode can include Al, Au, Ag, Ba, Yb, Ca, a lithium-aluminum alloy, a magnesium-silver alloy, indium tin oxide, gallium indium tin oxide, zinc indium tin oxide, titanium nitride or polyaniline. The electrode can be sandwiched, sputtered, or evaporated onto the energy converting region.

In some embodiments, a second electrode can be present in addition to the first electrode and the conductive polymer (Fig. 9c). In this case, the second electrode can be located on the substrate. However, in some embodiments, the conductive polymer can replace a second electrode. In these circumstances, the electrode can be a cathode and the conductive polymer can be an anode.

As previously stated, a second electrode can also be present. One possible configuration when the second electrode is present can be for the first electrode to be a cathode, the second electrode to be an anode and the conductive polymer to be part of the energy converting region. The second electrode can include indium tin oxide, gallium indium tin oxide, zinc indium tin oxide, titanium nitride or polyaniline.

The cathode can be patterned. The anode (i.e. the polymer or the second electrode) can also be patterned. The electrodes of the device can be connected to a voltage source by electrically conductive pathways.

The energy converting region can convert energy between photoenergy and electric energy. In particular, the energy converting region can convert photoenergy into electric energy. For a light absorbing device, light can strike the light absorbing device on the surface of the substrate. The substrate can be transparent or semi-transparent, allowing light to pass through to the energy converting region. As light interacts with the energy converting region, photons can be absorbed by the molecules, causing them to expel electrons and establishing a current. The energy converting region can include a light absorber, such as, for example, copper phthalocyanine, fullerene-C6o or bathocuprine. The energy converting region can also include silicon, copper indium diselenide, zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium oxide, magnesium sulfide, magnesium selenide, magnesium telluride, mercuric oxide, mercuric sulfide, mercuric selenide, mercuric telluride, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, lead telluride or combinations thereof. Specifically, the energy converting region can be a CuPc/C6o/BCP/Ag molecular organic heterojunction.

The energy converting region can include two or more layers of materials. The layers can be deposited on a surface of one of the electrodes by oxidative chemical vapor deposition, spin coating, dip coating, vapor deposition, sputtering, or other thin film deposition methods. The layers can include a p-type semiconductor and an n-type semiconductor. The layers can include a hole-injecting layer, a photoactive layer and/or an electron donating layer.

A material can be a photoactive material and include at least one dye. The photoactive material can include a plurality of dyes. Examples of dyes can include black dyes (e.g., tris(isothiocyanato)-ruthenium (II)-2,2':6',2"-terpyridine-4,4',4"-tricarboxylic acid, tris-tetrabutylammonium salt), orange dyes (e.g., tris(2,2'-bipyridyl-4,4'- dicarboxylato) ruthenium (II) dichloride, purple dyes (e.g., cis-bis(isothiocyanato)bis- (2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium (II)), red dyes (e.g., an eosin), green dyes (e.g., a merocyanine) or blue dyes (e.g., a cyanine). Examples of additional dyes include cyanines, xanthenes, anthraquinones, merocyanines, phenoxazinones, indolines, thiophenes, coumarins, anthocyanines, porphyrins, phthalocyanines, squarates, squarylium dyes, or certain metal-containing dyes. Combinations of dyes can also be used within a given region so that a given region can include more than one (e.g., two, three, four, five, six, seven) different dyes. The dye(s) can be sorbed (e.g., chemisorbed and/or physisorbed) on the nanoparticles. A dye can be selected, for example, based on its ability to absorb photons in a wavelength range of operation (e.g., within the visible spectrum), its ability to produce free electrons (or electron holes) in a conduction band of the nanoparticles, its effectiveness in complexing with or sorbing to the nanoparticles, and/or its color.

The layers can be optimized to absorb energy from photons within the spectrum of solar light. In other words, photons from the solar spectrum have energy within the band gap of the materials comprising the layers of the energy converting region. Different layers of the energy converting region may have band gaps corresponding to different portions of the solar spectrum. The solar spectrum can include electromagnetic radiation having a wavelength within the ultraviolet A region, ultraviolet B region, ultraviolet C region, visible light region, infrared A region, infrared B region or infrared C region.

Individual light absorbing devices can be formed at multiple locations on a single substrate to form a light absorbing system. The system can include devices that absorb photons from light of different wavelengths. The system can also include different substrates or conductive polymer.

Light absorbing devices can be incorporated into a number of apparatuses including, for example, curtains, shingles, architectural elements, artistic pieces, clothes, tents, portable power supplies, shelters, shoes, wallpaper, portable electronic devices (i.e. phones, calculators, radios, mp3 players) or newspapers.

Light absorbing devices (e.g., photovoltaics) can generate a voltage in response to illumination. The voltage produced can depend on a number of factors, including device materials and structure, and the nature of the illumination. For individual oCVD PEDOT devices, the voltage produced can be in the range of 0 V to 2 V or higher, 0.1 to 1.8 V, 0.2 to 1.5 V, or 0.5 to 1.0 V. In some cases, the voltage produced by an individual device can be in the range of 0.2 to 1.0 V. Individual devices can be electrically connected so as to produce a greater overall voltage; for example, cells connected in series each add voltage to the total circuit output. In general, a device including multiple device elements which are electrically connected can produce a voltage in the range of 0 to 100 V or higher, less than 1 V to 90 V, 2 V to 80 V, 5 V to 50 V, or 10 V to 20 V.

In some embodiments, 250 individual device elements, connected in series, can produce 75 V at 1 Sun of illumination. If desired, greater voltages can be produced with different device materials, circuit design, illumination, or combinations thereof. The overall voltage output of a device can be controlled by selection of the device materials, structure, electrical connections among device elements, illumination, or combinations thereof.

Flexible, transparent oCVD PEDOT layers can replace the conventional transparent conductive electrode (e.g., ITO) in organic PV devices on glass, plastic, and a variety of as-purchased fiber-based papers (Fig. 11). Although these substrates vary significantly in roughness and solvent affinity, no pretreatment steps were employed and the oCVD process was identical for each substrate. The well-documented CuPc/C6o(or PTCBI)/BCP/Ag molecular organic heterojunction architecture was chosen to

demonstrate a fully flexible, functional electronic device on these oCVD electrodes (Fig. 11a). See, for example, P. Peumans, S. R. Forrest, Appl. Phys. Lett. 79, 126 (2001); S. M. Schultes, et al , Mater. Sci. Eng., C 25, 858 (2005); and M. Brumbach, D. Placencia, N. R. Armstrong, /. Phys. Chem. C 112, 3142 (2008); each of which is incorporated by reference in its entirety. Importantly, all of these device layers were deposited and vapor- patterned at low temperature via vacuum thermal evaporation, and without the use of solvents, and thus were also compatible with all substrates described here.

For a light emitting device, the energy converting region can convert electric energy into photoenergy. A voltage can be applied between the two electrode on either side of the energy converting region. This can supply current, which can increase the energy of the molecules in the energy converting region and the molecules quickly release the energy as photons of light. The energy converting region can include poly(p- phenylene vinylene), polyfluorene, poly(fluorenylene ethynylene), poly(phenylene ethynylene), polyfluorene vinylene, or polythiophene. The energy converting region can also include silicon, copper indium diselenide, zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium oxide, magnesium sulfide, magnesium selenide, magnesium telluride, mercuric oxide, mercuric sulfide, mercuric selenide, mercuric telluride, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, lead telluride or combinations thereof.

The energy converting region can include two or more layers of materials. The layers can be deposited on a surface of one of the electrodes by oxidative chemical vapor deposition, spin coating, dip coating, vapor deposition, sputtering, or other thin film deposition methods. The layers can include a p-type semiconductor and an n-type semiconductor.

The energy converting region can include an electroluminescent or emissive material. The electroluminescent material can be selected for its emissive properties, such as emission wavelength or line width. The electroluminescent material can be a wide band gap material.

The electrical properties (such as band gaps and band offsets) of the energy converting region materials can be selected in combination with the device structure to produce a device where excitons are formed preferentially on the emissive material. The emissive material can transfer energy to an emission-altering material before light is emitted from the device. Energy transfer can occur by emission of light from the emissive material and reabsorption by the emission-altering material. Alternatively, the energy transfer can be a transfer of energy without light emission and reabsorption (such as Forster energy transfer). In either case, once the emission- altering material is in an excited state, it can emit light. In some circumstances, emission and reabsorption can be the primary method of energy transfer. When this is so, the emission-altering material need not be adjacent to the emissive material. The efficiency of Forster energy transfer, however, depends on the distance between the energy transfer partners, with smaller distances giving greater efficiency of energy transfer.

Devices can be prepared that emit visible or infrared light. Properties of semiconductor materials in the energy converting region can be selected such that the nanocrystal emits visible or infrared light of a selected wavelength. The wavelength can be between 300 and 2,500 nm or greater, for instance between 300 and 400 nm, between 400 and 700 nm, between 700 and 1100 nm, between 1100 and 2500 nm, or greater than 2500 nm.

Individual light emitting devices can be formed at multiple locations on a single substrate to form a display. The display can include devices that emit at different wavelengths. By patterning the substrate with arrays of different color-emitting semiconductor nanocrystals, a display including pixels of different colors can be formed.

The device can be made in a controlled (oxygen-free and moisture-free) environment, preventing the quenching of luminescent efficiency during the fabrication process. Other multilayer structures may be used to improve the device performance (see, for example, U.S. Patent No. 7,332,211 and U.S. Patent Application Publication No. 2004/0023010, each of which is incorporated by reference in its entirety). A blocking layer, such as an electron blocking layer ("EBL"), a hole blocking layer ("HBL") or a hole and electron blocking layer ("eBL"), can be introduced in the structure. A blocking layer can include 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-l,2,4-triazole ("TAZ"), 3,4,5-triphenyl-l,2,4-triazole, 3,5-bis(4-tert-butylphenyl)-4-phenyl-l,2,4-triazole, bathocuproine ("BCP"), 4,4\4''-Ms{N-(3-methylphenyl)-N-phenylamino}triphenylamine ("m-MTDATA"), polyethylene dioxythiophene ("PEDOT"), l,3-bis(5-(4- diphenylamino)phenyl-l,3,4-oxadiazol-2-yl)benzene, 2-(4-biphenylyl)-5-(4-tert- butylphenyl)- 1 ,3 ,4-oxadiazole, 1 ,3-bis[5-(4-( 1 , 1 -dimethylethyl)phenyl)- 1 ,3 ,4-oxadiazol- 2-yl]benzene, l,4-bis(5-(4-diphenylamino)phenyl-l,3,4-oxadiazol-2-yl)benzene, or 1,3,5- tris [5 -(4-( 1 , 1 -dimethylethyl)phenyl)- 1 ,3 ,4-oxadiazol-2-yl]benzene.

The applied voltage used for light generation can be an AC voltage or DC voltage. A DC voltage can be supplied by DC voltage generator, including, for example, a battery, a capacitor, or a rectified AC voltage. An AC voltage can be supplied by an AC voltage generator which produces a voltage waveform, such as, for example, a square wave. The waveform can have a frequency of between 0.01 Hz and 100 kHz, 10 Hz and 1 MHz, 250 Hz and 100 kHz, or 500 Hz and 10 kHz. The average voltage can be between 2 and 15 volts, or 3 and 8 volts. The percentage of duty cycle used can be calculated as one hundred multiplied by the average voltage divided by the maximum voltage. The percentage of duty cycle can be the relative time in an on/off cycle (in ) during which the voltage is on. The frequency, duty cycle, and peak voltage can be adjusted to optimize light output and stability from the device. Some applications of a duty cycle are described, for example, in G. Yu et al. Applied Physics Letters 73:111-113 (1998), incorporated herein by reference in its entirety. For example, the AC voltage waveform can be a 50% duty cycle at 5 V and 1 kHz, which has a maximum voltage of 5 volts, a frequency of 1 kHz, and an average voltage of 2.5 volts. In this way, a low average operating voltage can improve the operating half-lives of the devices. Device Encapsulation

A light absorbing or a light emitting device can be packaged or encapsulated to enhance device performance. Enhancing device performance can include increasing device lifetime, increasing mechanical robustness, and protecting the device from environmental damage, e.g. from oxygen, water, or contaminants. Enhancing device performance can also include increasing the range of conditions under which the device operates; for example, while an unpackaged device might be destroyed upon immersion in water, an encapsulated device can continue to function when submerged, because the encapsulant protects the device from water. Encapsulation or packaging can be done with a wide variety of materials, but in general, transparent materials are preferred, e.g., glass or plastic. Plastic can be particularly preferred because the packaged device can retain flexibility, one of the desirable properties of the unpacked device. The packaging can be applied in a number of ways, including dipping, roll coating, vapor deposition, laminating, heat sealing, vacuum sealing, or by polymerization, including, for example, initiated CVD (iCVD)

polymerization. Particular materials suitable for device encapsulation include but are not limited to lamination film (e.g., as used in offices for laminating paper), parylene-C, and poly(lH,lH,2H,2H-perfluorodecyl acrylate) (PFDA).

Examples

Electrical Property Calculations

The use of a substrate-independent vapor printing process to deposit the conducting polymer poly(3,4-ethylenedioxythiophene) in place of the conventional transparent conductive electrode (e.g., indium-tin oxide (ITO)) in organic solar cells on glass, plastic, and paper substrates was examined. This process can combine oxidative chemical vapor deposition (oCVD) with in situ shadow masking to create well-defined polymer patterns on the surface of choice (Fig. 23a, inset and Figs. 5 and 6). (M. E. Alf, et al., Adv. Mater. 2010, 22, 1993; S. H. Baxamusa, et al., Phys Chem Chem Phys 2009, 11, 5227, each of which is incorporated by reference in its entirety). For oCVD, the polymerized thin films can form by simultaneous exposure to vapor-phase monomer (EDOT) and oxidant (FeCls) reactants at low substrate temperatures (20-100°C), moderate vacuum (-0.1 Torr). The printed polymer patterns (down to 20 μιη resolution) can result from the presence of a shadow mask by maintaining the partial pressure of the vapor-delivered oxidant species sufficiently close to its saturation pressure at the substrate, which can prevent significant mask undercutting. The vapor delivery of the oxidant species can make this process unique from other techniques that rely on solvent casting of oxidants prior to vapor delivery steps. (B. Winther- Jensen, K. West, Macromolecules 2004, 37, 4538; S. Admassie, et al., Sol. Energy Mater. Sol. Cells 2006, 90, 133, each of which is incorporated by reference in its entirety). Because the process is all dry, there may be no wettability or surface tension effects on rough substrates like paper, and exactly the same process steps can be used to fabricate devices on glass, plastics, and papers. For use as a transparent electrode, the conducting polymer layer can provide both low sheet resistance (¾) and high optical transmittance (7) which are related by the following equation:

where Zo is the impedance of free space (377 Ω), and Od_C and σ_ορ are the optical and dc conductivities, respectively. (V. Scardaci, R. Coull, J. N. Coleman, Appl. Phys. Lett., 97; Y. Hyun Kim, et al., Adv. Funct. Mater. 2011, XX, 1., each of which is incorporated by reference in its entirety). Figure la shows this relationship for oCVD PEDOT deposited on glass at 80°C and 0.1 Torr. The data fit well to equation 1 across the full data range, giving This value can be comparable to the best commercially available conducting polymer solutions and can be slightly lower than that reported for carbon nanotube conductors Od_C o_op~15 and traditional metal oxide electrodes Od_C/o_op~35.

The integration of oCVD PEDOT anodes into thin-film organic PV devices on smooth glass surfaces using the well-documented CuPc/C₆o (or PTCBI)/BCP/Ag molecular organic heterojunction architecture was first established (Fig. 23b, inset). (P. Peumans, S. R. Forrest, Appl. Phys. Lett. 2001, 79, 126; P. Peumans, et al., /. Appl. Phys. 2003, 93, 3693; S. M. Schultes, et al., Mater. Sci. Eng., C 2005, 25, 858; F. Yang, et al., Adv. Mater. 2007, 19, 4166; N. Li, S. R. Forrest, Appl. Phys. Lett. 2009, 95, each of which is incorporated by reference in its entirety).

Fig. 23b compares representative current density- voltage characteristics for individual devices on glass and differing only in anode structure: (i) oCVD PEDOT (50 nm), (ii) indium tin oxide (ITO), (iii) ITO/oCVD PEDOT (10 nm), (iv)

ITO/PEDOT:poly(styrenesulfonate (PSS). The series resistance (R_s) and parallel (shunt) resistance (R_p) were determined (Table SI) by fitting the dark current across the voltage range to the generalized Shockley diode equation:

where n is the diode ideality factor and J_s is the reverse saturation current. (B. P. Rand, D. P. Burk, S. R. Forrest, Physical Review B 2007, 75, which is incorporated by reference in its entirety). The devices incorporating oCVD anodes (i and iii) can perform comparably to the devices with conventional ITO anode structures (ii and iv), and both oCVD PEDOT and PEDOT:PSS devices can exhibit improved open-circuit voltage (0.48V) relative to those on bare ITO (0.41V). (P. Peumans (2004); N. R. Armstrong, et al., Thin Solid Films 2003, 445, 342; H. J. Snaith, et al., Polymer 2005, 46, 2573, each of which is incorporated by reference in its entirety). Both oCVD PEDOT and PEDOT:PSS can have comparable work functions (-5.2 eV); however, the conductance of oCVD PEDOT thin films can be several orders of magnitude more conductive than the PEDOT:PSS (CLEVIOS™ P VP Al 4083) buffer layer (<10 S-cm-1), which can contribute to the higher observed fill factor (>0.6) in the devices with ITO/oCVD PEDOT electrodes (iii) due to the lower device series resistance (1.2 Ω-cm² vs. 4.2 Ω-cm²). For the ITO-free oCVD electrodes (i), the trade-off between sheet resistance and transparency with thickness can account for the decrease in the fill factor (0.54) due to series resistance (4.4 Ω-cm²) and the short-circuit current (3.8 mA-cm²) relative to (ii) (Supporting Table SI). Finally, the power lost due to the electrode sheet resistance for a cell of width w and length /, where current is collected along / can be estimated by the following equation:

¹ ha —

(M. W. Rowell, et al., Appl. Phys. Lett. 2006, 88, which is incorporated by reference in its entirety). For the PEDOT electrodes, this can correspond to less than 1% fraction of power lost (P_/oss/generated total power) for these 0.5x2.0 mm² cells, and to prevent a power loss of over 10% the cells can be each be kept below 5 mm wide.

Deposition of oCVD polymer electrodes.

The oCVD process procedure and the reactor configuration used have been previously described. (Baxamusa, S. H., Im, S. G., Gleason, K. K., Initiated and oxidative chemical vapor deposition: a scalable method for conformal and functional polymer films on real substrates. Phys Chem Chem Phys 11, 5227 (2009); Alf, M. E. et al., Chemical Vapor Deposition of Conformal, Functional, and Responsive Polymer Films. Adv. Mater. 22, 1993 (2010); and Im, S. G., Gleason, K. K., Systematic control of the electrical conductivity of poly(3,4-ethylenedioxythiophene) via oxidative chemical vapor deposition. Macromolecules 40, 6552 (2007), each of which is incorporated by reference in its entirety.) The same reaction conditions were used for all substrates in this study. The substrate temperature was maintained elevated at ~80°C by a PID controller to help enhance the film conductivity. (Im, S.G., (2007)). The process pressure was maintained at -100 mTorr. The flow rate of evaporated 3,4-ethylenedioxythiophene monomer (Aldrich, 97%) was metered at ~5 seem and FeCl₃ oxidant (Aldrich) was controllably evaporated from a resistively heated crucible at ~250°C. The thickness of oCVD PEDOT electrodes were determined by limiting the time of reaction (~5 min for a 50-nm thick film). oCVD PEDOT anodes were deposited for thin film and OPV characterization on pre-cleaned glass (described below) and various other substrates, which were used as received: PET (5-mil Melinex® Q65FA, Dupont), printer paper (Office Depot, 20 lb, 92 brightness, #99964200), tissue paper (Office Depot, #48601-OD), tracing paper (Canson, 25 lb, #702-321), newsprint (Paeon Papers, #3407), Reynolds® Cut-Rite® Wax Paper, and Saran™ Premium Wrap (SC Johnson).

Electrode characterization.

Electrode thickness was measured with a Tencor P-16 profilometer and the sheet resistance was measured using a Signatone S-302-4 four-point probe station with a Keithley 4200-SCS semiconductor characterization system. The conductivity was calculated from the sheet resistance and measured thickness. The optical transmission of the polymer electrodes was measured on glass using a Varian Cary 6000i UV-Vis-NIR spectrophotometer. Flex testing for ITO/PET (Aldrich, 5-mil PET with 1000 A ITO, 60 Ω D ^"1) and oCVD PEDOT electrodes on PET was performed using an in-house flexing- test system, and the sheet resistance was measured between each flexing iteration.

Stretch testing was performed using a MTS Nano Instruments Nano-UTM nanotensile tester. 5 mm x 1 mm oCVD PEDOT electrodes on Saran™ wrap were anisotropically stretched by 0.01 mm increments at a strain rate of 0.005 s^"1 while the resistance across the electrode (in the direction of extension) was simultaneously measured using an

Agilent U125A multimeter attached to the polymer electrode using conductive tape and alligator clips. The stretching extension was defined as the change in length of the electrode divided the initial length (AL/Lo), and the conductivity was calculated assuming a constant film volume as described in the literature. (Hansen, T. S., West, K., Hassager, O., Larsen, N. B., Highly stretchable and conductive polymer material made from poly (3,4-ethylenedioxythiophene) and polyurethane elastomers. Adv. Funct. Mater. 17, 3069 (2007), which is incorporated by reference in its entirety). The electrode adhesion on the PET and Saran™ wrap substrates was also confirmed by tape testing (ASTM D3359-97), and the surface after flexing and stretching was imaged using an Olympus CX41 optical microscope with a maximum magnification of xlOO. Electrode foldability was tested on -100 nm oCVD PEDOT electrodes deposited on untreated newsprint; the film thickness was based on films deposited on glass slides from the same deposition. The folding tests (±180°) were performed by creasing the paper/electrode flat using gentle pressure applied with a pencil eraser; for folding at +180°, the crease was made between two additional sheets of paper to prevent contact between the eraser and the polymer electrode. After each iteration, the paper was completely flattened back to 0° and the sheet resistance was measured across the crease with a multimeter with probe spacing of 1 cm (0.5 cm on either side of the crease).

OPV device fabrication.

Pre-patterned ITO/glass substrates were obtained from Thin Film Devices (sheet resistance = 20 Ω/D). The bare glass and the ITO/glass substrates were first cleaned by sequential 5 minute ultrasonications in deionized water/detergent solution (Micro-90), deionized water, acetone, and boiling isopropyl alcohol, and then exposed to oxygen plasma for 1 minute (100 W, Plasma Preen, Inc.). For the control devices, PEDOT:PSS solution (CLEVIOS™ P VP AI 4083) was filtered (0.45 μιη), spin-coated at 4000 rpm for 60 seconds, annealed at 210°C for 5 minutes in air, and finally exposed to oxygen plasma for <5 seconds (100 W, Plasma Preen, Inc.). All substrates were then transferred to an evaporation chamber (<10^~6 Torr) where the organic active layers (CuPc, C₆o, and BCP) and Ag cathodes were thermally evaporated through a shadow mask at rates of ~1 A s^"1, measured using a calibrated quartz crystal microbalance. The overlap area between the anode and cathode defined the device area which ranged from 0.005 to 0.01 cm². The copper phthalocyanine (CuPc, Acros Organics, ca. 95% purity), fullerene-C6o (C₆o, Luminescence Technology Corp., >99.5%) and bathocuprine (BCP, Sigma Aldrich, 99.99%) were each purified once via thermal gradient sublimation, and the Ag (Alfa Aesar, 1-3 mm shot, 99.9999%) was used as received.

To eliminate the possibility of performance variation due to fabrication conditions, all oCVD-based devices are fabricated and tested in parallel with control devices, which were grown on ITO-coated glass substrates with structure ITO (100 nm)/PEDOT:PSS (70 nm)/CuPc (20 nm)/C₆₀ (40 nm)/BCP (12 nm)/Ag (1000 nm). OPV device characterization.

The J-V characteristics of the OPV cells were measured in nitrogen atmosphere using a custom probe fixture with an Agilent 4156C Precision Semiconductor Parameter Analyzer and simulated AM 1.5 solar illumination from a Newport 91191 lkW solar simulator. Opaque masks were used to selectively illuminate the active cell area, and optical density filters were used to achieve the desired intensity as measured with a calibrated Si photodiode. After testing, the exact device areas were measured with an optical microscope and used to calculate current density. Series and shunt resistances were estimated as the inverse slope of the J-V curve at V=+1.2V and 0V, respectively.

The external quantum efficiency (EQE) spectra of individual photovoltaic cells were measured in nitrogen atmosphere with a Stanford Research Systems SR830 lock-in amplifier, under a focused monochromatic beam of variable wavelength light generated by an Oriel lkW xenon arc lamp coupled to an Acton 300i monochromator and chopped at 43 Hz. A Newport 818-UV calibrated silicon photodiode was used to measure the incident monochromatic light intensity. Internal quantum efficiency (IQE) spectra were calculated by dividing the EQE by the fraction of incident light absorbed by the active layers (Figs. 18-19). The total active layer absorption was measured as the difference between the percentage of incident light reflected by the substrate/anode/ Ag structure and the percentage reflected by the complete device structure as measured with a Cary 500i UV-Vis-NIR dual-beam spectrophotometer with a PTFE-coated integrating sphere attachment.

The current- voltage characteristics of the large-area, series -integrated photovoltaic arrays were tested in air with an HP 4145B Semiconductor Parameter Analyzer using AM 1.5 solar illumination from a Oriel 94023 A 450W solar simulator at 80 mW-cm^"2 (Figs. 12, 13a, 13c, 13d, 21, 21, and 22b) as measured with a calibrated silicon photodiode. Spatial distribution maps were measured by probing the anode and cathode of each individual cell at both short circuit and open circuit under the same lighting conditions. Finally, the lifetime characteristics of the full packaged and unpackaged arrays were measured by accelerated aging in air through exposure to constant illumination (80 mW-cm ² halogen lamp) and elevated temperature (42 °C/108 °F) at open-circuit while the current-voltage characteristics were measured periodically (Figs. 13a, 21), as described above. Example 1: CVD Deposition and Characterization of PEDOT Films.

PEDOT depositions were carried out in a custom-built vacuum chamber that has been described elsewhere and is depicted in Fig. 8. (D. D. Burkey, K. K. Gleason, J Appl Phys 93, 5143 (2003); H. G. Pryce-Lewis, D. J. Edell, K. K. Gleason, Chem Mater 12, 3488 (2000), which is incorporated by reference in its entirety). Glass slides and silicon wafers were used for substrates. The stage was regulated with cooling water and was normally kept at 34 °C. A stage heater was available when stage temperatures greater than room temperature were desired. The stage was also configured to be biased with a DC Voltage using a Sorenson DCS 600-1.7 power supply. The chamber pressure was controlled by a butterfly valve connected to an MKS model 252-A exhaust valve controller and was maintained at approximately 300 mTorr. Fe(III)Cl₃ (97%, Aldrich) was selected as the oxidant. The powder was loaded in a porous crucible with a nominal pore size of 7 μιη and positioned above the stage. The crucible was heated to a temperature of about 240 °C, where sublimation of the oxidant begins to occur. Argon (Grade 5.0, BOC Gases) was delivered into the crucible as a carrier gas for the Fe(III)Cl₃ vapors. An argon flow rate of 2 seem was set using an MKS mass flow controller with a range of 50 seem N₂. Once a yellow film of Fe(III)Cl₃ was observed on the substrate, the crucible temperature was reduced to end sublimation. EDOT monomer (3,4- ethylenedioxythiophene, Aldrich) heated to 100 °C was then introduced into the reactor through heated lines and using an MKS 1153 mass flow controller set at 95 °C. The

EDOT flow rate was normally 10 seem. Pyridine (99%, Aldrich) at room temperature was evaporated into the reactor using a needle valve to control the flow rate. A deposition time of 30 minutes was used for all of the films.

After deposition, the films were dried for at least 2 hours in a vacuum oven heated to 80 °C at a gauge pressure of -15 in.Hg. The thickness of the films deposited on glass was measured on a Tencor P-10 profilometer and conductivity measurements were done with a four-point probe (Model MWP-6, Jandel Engineering, Ltd). Films on silicon substrates were measured with FTIR (Nexus 870, Thermo Electron Corporation) for information on chemical composition. Deposited films were sometimes rinsed in methanol (HPLC Grade, J. T. Baker) or in a 5 mM dopant solution of nitrosonium hexafluorophosphate, NOPF₆, (96%, Alfa Aesar) in acetonitrile (ACS Grade, EMT). The rinse step was intended to remove any unreacted monomer or oxidant in the films as well as short oligomers and reacted oxidant remaining in the form of Fe(II)Cl₂. After rinsing, the films changed from a cloudy light yellow color to a sky blue hue.

Electrochemical testing took place in an aqueous 0.1 M solution of sulfuric acid (VWR). The CVD PEDOT film on ITO was the working electrode, platinized copper was the counter electrode, and a saturated calomel electrode (SCE) was used as the standard. A potentiostat (EG&G Printon Applied Research Model 263A) scanned from - 0.4 V to 0.6 V based on preliminary cyclovoltammograms. In-situ UVNIS was conducted using an optical fiber to couple light from a StellarNet SLI light source with a tungsten krypton bulb emitting from 350 to 1700 nm. The spectrometer was a StellarNet EPP 2000 having a detector with a range spanning 190 to 2200 nm.

Example 2: Deposition on Fragile Substrates.

The conductive polymers have been deposited on a number of substrates with no pre- or post-treatment, even a ~10-μιη thick sheet of SARAN™ wrap (Fig. lb, left). In contrast, drop-cast conducting polymer formulation CLEVIOS™ PH 750 (>650 S cm^"1 as a dried film) did not wet this hydrophobic surface (Fig. lb, right). While oxygen plasma pretreatment has been reported to enhance wettability, this additional step can also add cost and can easily degrade the mechanical, chemical, and morphological properties of fragile substrates. The conductive polymers also formed on substrates that would be destroyed or dissolved by solvents, such as absorbent and water-soluble papers, (e.g. bathroom tissue and rice paper, respectively; Figs. 5 and 6).

To demonstrate the versatility of oCVD-deposited electrodes, OPVs were fabricated directly on various fiber-based paper substrates (Figs. 2d-lll). Paper substrates have a range of light transmission properties, typically characterized by high light scattering (transmissive and reflective) and low absorptive losses (Fig. 17). The surface reflectivity was evident in the J-V curves for PVs on various papers (Fig. 11D), in which the short-circuit currents scaled inversely with losses due to reflection (Fig. 17). This was also evident by comparing the quantum efficiency and absorption spectra for oCVD PEDOT devices on tracing paper with conventional glass/ITO devices (Figs. HE, 18, and 19).

With regard to Fig. 18, total active layer absorption in CuPc/C60 heterojunction devices on (Figs. 18a- 18b) paper/oCVD PEDOT and (Figs. 18c- 18d)

glass/ITO/PEDOT:PSS was measured. The device structure was [CuPc (80 nm)/C60 (40 nm)/BCP (10 nm)/Ag (150 nm)] and the oCVD PEDOT thickness was 50 nm. The active layer absorption ( AACT) was measured as the difference between the percentage of incident light reflected by the substrate/anode/ Ag structure ( RSUBS) and the percentage reflected by the complete device structure ( RTOT)- The results are shown for both total reflection (Figs. 18a, 18c) and specular reflection (Figs. 18b, 18d) to illustrate the high contribution of scattered light to active layer absorption in paper-based cells; however, the total absorption spectra were used to calculate the internal quantum efficiency spectra (see Fig. HE).

With regard to Fig. 19, total active layer absorption in CuPc/PTCBI

heterojunction devices on (Figs. 19a- 19b) paper/oCVD PEDOT and (Figs. 19c-19d) glass/ITO/PEDOT:PSS was measured. The device structure was [CuPc (80 nm)/PTCBI (40 nm)/BCP (10 nm)/Ag (150 nm)] and the oCVD PEDOT thickness was 50 nm. The active layer absorption ( AACT) was measured as the difference between the percentage of incident light reflected by the substrate/anode/ Ag structure ( RSUBS) and the percentage reflected by the complete device structure ( RTOT)- The results are shown for both total reflection (Figs. 19a, 19c) and specular reflection (Figs. 19b, 19d) to illustrate the high contribution of scattered light to active layer absorption in paper-based cells; however, the total absorption spectra were used to calculate the internal quantum efficiency spectra (see Fig. He).

While the external quantum efficiencies (charges collected per incident photons) were significantly lower on the paper substrates due to substrate/electrode losses, the internal quantum efficiencies (charges collected per absorbed photons) were comparable across the visible spectrum, suggesting similar upper bounds on efficiency for both the paper and conventional ITO/glass structures if effective light trapping schemes are incorporated. We note that such schemes may be uniquely designable for paper substrates because of their good reflectance and scattering (non-specular) properties, where >90 of the light absorbed by the active layer in the paper-based devices stems from diffuse transmission (scattering) compared to <10 on smooth ITO/glass (Figs. 17-19). Example 3: oCVD PEDOT Electrodes.

oCVD PEDOT (poly(3,4-ethylenedioxythiophene)) electrodes can successfully replace the conventional indium tin oxide (ITO) anodes in organic photovoltaic devices (Fig. 2a, inset) fabricated with the well-studied CuPc/C6o/BCP/Ag molecular organic heterojunction architecture. (Peumans, P., Forrest, S. R., Very-high-efficiency double- heterostructure copper phthalocyanine/C-60 photovoltaic cells. Appl. Phys. Lett. 79, 126 (2001); Schultes, S. M., Sullivan, P., Heutz, S., Sanderson, B. M., Jones, T. S., The role of molecular architecture and layer composition on the properties and performance of CuPc-C-60 photovoltaic devices. Mater. Sci. Eng., C 25, 858 (2005); and Brumbach, M., Placencia, D., Armstrong, N. R., Titanyl phthalocyanine/C-60 heterojunctions: Band-edge offsets and photovoltaic device performance. J. Phys. Chem. C 112, 3142 (2008), each of which is incorporated by reference in it entirety). Importantly, all of the other device layers can also deposited at low temperature and without the use of solvents, via vacuum thermal evaporation, allowing us to employ a versatile array of substrates. To eliminate the possibility of performance variation due to fabrication conditions, all oCVD-based devices were fabricated and tested in parallel with control devices, with structure ITO (100 nm)/PEDOT:PSS (70 nm)/CuPc (20 nm)/C₆₀ (40 nm)/BCP (12 nm)/Ag (1000 nm).

Fig. 2a compares representative current density- voltage (J-V) characteristics for OPVs on glass differing only in anode structure: (i) oCVD PEDOT, (ii) ITO, (iii)

ITO/oCVD PEDOT, (iv) ITO/PEDOT:PSS. The devices incorporating oCVD anodes (i and iii) performed comparably with the conventional anode structures (ii and iv), and both exhibited improved open-circuit voltage relative to bare ITO. This suggested that the oCVD layers can provide an advantageous work function and/or morphological benefit, analogous to behavior observed for PEDOT:PSS buffer layers. (Peumans, P., Forrest, S. R., Very-high-efficiency double-heterostructure copper phthalocyanine/C-60 photovoltaic cells. Appl. Phys. Lett. 79, 126 (2001); Armstrong, N. R. et al., Interface modification of ITO thin films: organic photovoltaic cells. Thin Solid Films 445, 342 (2003); and Snaith, H. J., Kenrick, H., Chiesa, M., Friend, R. H., Morphological and electronic consequences of modifications to the polymer anode 'PEDOT : PSS'. Polymer 46, 2573 (2005), each of which is incorporated by reference in its entirety.) While both oCVD PEDOT and PEDOT:PSS have comparable work functions (-5.2 eV) 15, the oCVD electrode was orders of magnitude more conductive than the PEDOT:PSS buffer layer (<10 S cm^"1). Indeed, the ITO/oCVD PEDOT electrodes (iii) exhibited the highest fill factor (>0.6) of the devices tested. This can be consistent with a reduction in device series resistance relative to ITO/PEDOT:PSS (iv) (Table 1). For the ITO-free oCVD electrodes (i), there was a trade-off between sheet resistance and transparency with thickness (Fig. 2b), which may account for the small differences in fill factor and short circuit current relative to (ii) (Table 1).

Table 1. Solar cell parameters for OPVs with different anode layers.

Jsc Fill ^series Rshunt

Anode Material (niA cm^"2) V_0C (V) Factor (Ω-cm²) (Ω-cm²)

oCVD PEDOT 3.2 0.44 0.54 5.0 0.8 xlO³

ITO 4.4 0.41 0.57 0.6 1.0 xlO³

ITO/oCVD PEDOT 4.1 0.48 0.60 1.2 1.2 xlO³

ITO/PEDOT:PSS 4.2 0.47 0.56 7.2 1.1 xlO³

Uniquely, oCVD conducting polymers can be in situ covalently bonded (grafted) to flexible substrates possessing aromatic functional groups upon film formation (e.g. on common polystyrenes (PS) and polyethylene terephthalates (PET)). The superior adhesion of the grafted films can be desirable for roll-to-roll processing and for flexible and stretchable electronics, where mechanical stresses could otherwise result in catastrophic cracks or delamination. Indeed, after 1000 flexing cycles at <5 mm radius (Fig. 3a), the electrical conductivity of oCVD PEDOT on a PET substrate was minimally affected while that of commercial ITO-coated PET decreased over 400-fold due to severe crack formation (Fig. 3a, inset), a direct result of the brittle nature of the ITO and relatively weak substrate adhesion. (Cairns, D. R. et al., Strain-dependent electrical resistance of tin-doped indium oxide on polymer substrates. Appl. Phys. Lett. 76, 1425 (2000), which is incorporated by reference in its entirety). In contrast, the oCVD PEDOT exhibited no cracking and maintained its electrical conductivity even through extreme flexes at a radius <1 mm. Moreover, after over 100 flexing cycles, OPVs with oCVD PEDOT electrodes (i) on PET, displayed no noticeable change in performance (Fig. 3b). Thus, the flexibility of the oCVD electrode may have allowed the subsequent device layer to retain its integrity upon flexing. This was strong contrast to reports for "flexible" ITO- based OPVs in which electrode cracking propagated through the device, ultimately resulting in shorting. (Na, S. I., Kim, S. S., Jo, J., Kim, D. Y., Efficient and Flexible ITO- Free Organic Solar Cells Using Highly Conductive Polymer Anodes. Adv. Mater. 20, 4061 (2008), which is incorporated by reference in its entirety).

The stretchability of oCVD PEDOT electrodes was exhibited on common Saran™ wrap (~10-μιη thick) (Fig. 3c). The oCVD PEDOT was also covalently bonded to this PET-based substrate, inhibiting slippage and ensuring that the polymer electrode was stretched along with the substrate. Under moderate stretching (up to 25% extension) the conductivity steadily increases, most likely due to molecular chain alignment, as has been reported for other conducting polymer films. (Ogasawara, M., Funahashi, K., Demura, T., Hagiwara, T., Iwata, K., Enhancement of Electrical-Conductivity of Polypyrrole by Stretching. Synth. Met. 14, 61 (1986); and Hansen, T. S., West, K., Hassager, O., Larsen, N. B., Highly stretchable and conductive polymer material made from poly (3,4- ethylenedioxythiophene) and polyurethane elastomers. Adv. Funct. Mater. 17, 3069 (2007), each of which is incorporated by reference in its entirety). The conductivity then slowly declined; however, significant electrical conductance was maintained until there was mechanical failure of the underlying substrate at nearly 200%. This exceeded the stretchability of typical metals, ITO, graphene, and even "wavy" silicon ribbons

(electrical failure at -5-30% extension) and was comparable to some of the best reports for conducting polymer films and composites (electrical failure at -100-200% extension). (Cairns, D. R. et al., Strain-dependent electrical resistance of tin-doped indium oxide on polymer substrates. Appl. Phys. Lett. 76, 1425 (2000); Hansen, T. S., West, K., Hassager, O., Larsen, N. B., Highly stretchable and conductive polymer material made from poly (3,4-ethylenedioxythiophene) and polyurethane elastomers. Adv. Funct. Mater. 17, 3069 (2007); Li, T., Huang, Z. Y., Suo, Z., Lacour, S. P., Wagner, S., Stretchability of thin metal films on elastomer substrates. Appl. Phys. Lett. 85, 3435 (2004); Kim, K. S. et al., Large-scale pattern growth of graphene films for stretchable transparent electrodes.

Nature 457, 706 (2009); Rogers, J. A., Someya, T., Huang, Y. G., Materials and

Mechanics for Stretchable Electronics. Science 327, 1603; Sekitani, T. et al., A rubberlike stretchable active matrix using elastic conductors. Science 321, 1468 (2008); Urdaneta, M. G., Delille, R., Smela, E., Stretchable electrodes with high conductivity and photo- patternability. Adv. Mater. 19, 2629 (2007), each of which is incorporated by reference in its entirety). Microscopic cracks gradually formed and became larger as the film was stretched, which interrupted the current conduction along the stretch direction; there were, however, complete conducting polymer pathways visible even at 150% extension (Fig. 3c, lower).

The foldability of oCVD PEDOT electrodes on paper substrates was demonstrated by repeatedly creasing the electrodes (Fig. 3d). After an initial decrease over the first -10 creases, the conductivity levels fell off at 50-150 S cm , and significant conductance was retained after over 100 folding iterations. This was in contrast to evaporated metal films, which exhibited complete electrical failure after fewer than 10 folding iterations. (Siegel, A. C. et al., Foldable Printed Circuit Boards on Paper Substrates. Adv. Funct. Mater. 20, 28 (2010), which is incorporated by reference in its entirety). Moreover, conductivities on paper that are comparable to planar films grown on glass substrates during the same deposition cycle were observed. This was remarkable, considering the oCVD film thickness was much less than the RMS surface roughness of the paper (-2-4 μιη). The high conductivity of oCVD PEDOT on such a highly non-planar surface and its endurance to repeated folding iterations may be rooted in the ability of the vapor-phase oCVD process to penetrate into the fibers of the paper substrate and create a partially conformal coating throughout the fiber matrix. This may impart good mechanical and electrical connectivity.

OPVs were also fabricated directly on various as-purchased paper substrates. The transparent polymer electrodes were conformally deposited on the delicate paper fibers without any pretreatment steps or protecting layers. The versatility of this ability can be hard to match by any other thin-film deposition technique. To help prevent electrical shorting through the nonconformally evaporated active layers, the thickness of the CuPc layer was increased from 20 nm to 100 nm. (Yang, F., Shtein, M., Forrest, S. R., Controlled growth of a molecular bulk heteroj unction photovoltaic cell. Nature Mater. 4, 37 (2005), which is incorporated by reference in its entirety.) The low transparency of the paper substrates along with the high CuPc absorption may have inhibited the intensity of light illuminating the OPV within an exciton diffusion length of the photoactive heterojunction. Thus, for these devices the paper-substrates were illuminated with high- intensity 500 mW cm^"2 simulated solar illumination to illuminate the photoactive interface as close as possible to intensities typical of OPVs on glass/ITO under 100 mW cm^"2 illumination. Characteristic J-V performance curves (Fig. 4a) showed significant power generation for completed OPVs on tracing paper (b), tissue paper (c), and printer paper (d). The relatively low open-circuit voltage as compared to the standard glass-based devices was likely a result of increased current pathways through the nonconformal photoactive layers that allow facile charge transport opposite the photo-generated current. The short circuit currents scaled with substrate transparency, which was expected;

however, they were relatively high considering the absorptive substrate and thick CuPc layer, suggesting there may be enhanced light utilization due to favorable scattering through the roughened substrate and interfaces. The foldability of these devices as well as their ultra- light weight was evident. Ultrathin paper substrates (e.g., tissue paper) weigh ~10^~3 g cm^"2, in comparison to -10^"1 g cm^"2 for a crystalline Si wafer and ~10^"2 g cm^"2 for a conventional 5 mil PET plastic substrate. Although the efficiency of the ultrathin paper-based devices was lower than state-of-the-art solar modules, they exhibited high power-to-weight ratios of up to 550 W kg^"1 under these testing conditions, and continued improvements in the cell efficiency may further extend their light-weight advantage. The devices were also easily patterned over large areas and maintained photovoltaic power generation after folding into three- dimensional structures. Fig. 4g shows a thin-film photovoltaic cell integrated into the wings of a paper airplane on a -50 cm² sheet of tracing paper that was first patterned with the oCVD-enabled device structure. The oCVD fabrication process was also compatible with other common papers, such as newsprint, without disturbing the underlying printed ink (Fig. 4e), and even wax paper (Fig. 4f), which was resistant to or damaged by common solvents.

The nondestructive oCVD method enabled rapid fabrication of highly conductive, flexible, adherent, and transparent polymer electrodes from earth-abundant elements on virtually any substrate, including delicate papers and plastics for large-area applications. Integration into OPV structures resulted in ITO-free devices having comparable performance to control devices that utilize industry standard materials and processes. The versatility of the oCVD conducting polymers was illustrated by organic solar cells on a variety of as-purchased "everyday" paper substrates, including printer paper, tissue paper, and tracing paper, fabricated without any pretreatment steps or protecting layers, and exhibiting power-to-weight ratios over 500 W kg^"1. The oCVD conducting polymer electrodes maintained their high conductance even when flexed (>1000 times), creased (>100 times), and stretched (-200%), far exceeding the durability of ITO and other standard electrode materials. Beyond the applications in OPV structures, oCVD polymers can be similarly integrated in other large and small-area optoelectronic device structures. Moreover, as the existing library of electrically and optically active oCVD polymer chemistries grows, the power of this technique may increase accordingly and it may be readily possible to make complete devices conformally on complex and delicate substrates for novel architectures and ultimately improved performance. Example 4: OPVs on glass

Fig. lib compares representative current density- voltage (J-V) characteristics for OPVs on glass and differing only in anode structure: (i) oCVD PEDOT, (ii) ITO, (iii) ITO/oCVD PEDOT, (iv) ITO/PEDOT:PSS. The devices incorporating oCVD anodes (i and iii) perform comparably to the devices with conventional ITO anode structures (ii and iv), and both oCVD PEDOT and PEDOT:PSS devices exhibit improved open-circuit voltage relative to OPVs on bare ITO (see, for example, P. Peumans, S. R. Forrest, Appl. Phys. Lett. 79, 126 (2001); N. R. Armstrong et al , Thin Solid Films 445, 342 (2003); and H. J. Snaith, H. Kenrick, M. Chiesa, R. H. Friend, Polymer 46, 2573 (2005); each of which is incorporated by reference in its entirety). Both oCVD PEDOT and PEDOT:PSS have comparable work functions (-5.2 eV) (M. E. Alf et al. , Adv. Mater. 22, 1993 (2010), which is incorporated by reference in its entirety); however, oCVD PEDOT thin films were previously shown to be several orders of magnitude more conductive than the PEDOT:PSS (CLEVIOS™ P VP AI 4083) buffer layer (<10 S cm^"1) (S. H. Baxamusa, S. G. Im, K. K. Gleason, Phys Chem Chem Phys 11, 5227 (2009), which is incorporated by reference in its entirety). This contributed to the higher observed fill factor (>0.6) in OPVs with ITO/oCVD PEDOT electrodes (iii), due to the lower device series resistance (see Table 1, above). For the ITO-free oCVD electrodes (i), there was a trade-off between sheet resistance and transparency with thickness (Fig. 10c), which accounted for the small differences in the fill factor and the short-circuit current relative to (ii) (Table 1).

Moreover, after over 100 flexing cycles, OPVs with oCVD PEDOT electrodes (i) on PET, displayed no significant change in performance (Fig. 11c). The flexibility of the oCVD electrode allowed the subsequent device layer to retain their integrity upon flexing, a strong contrast to reports for "flexible" ITO-based OPVs in which electrode cracking propagates through the device, ultimately resulting in electrical shorting (S. I. Na, S. S.

Kim, J. Jo, D. Y. Kim, Adv. Mater. 20, 4061 (2008), which is incorporated by reference in its entirety) (Fig. 15).

With regard to Fig. 16, the oCVD PEDOT was covalently bonded to Saran™ Wrap (a PET-based substrate), inhibiting slippage and ensuring that the polymer electrode was stretched along with the substrate. Under moderate stretching (up to 25% extension) the conductivity steadily increased, most likely due to molecular chain alignment, as has been reported for other conducting polymer films (see, for example, T. S. Hansen, K. West, O. Hassager, N. B. Larsen, Adv. Funct. Mater. 17, 3069 (2007); and M. Ogasawara, K. Funahashi, T. Demura, T. Hagiwara, K. Iwata, Synth. Met. 14, 61 (1986); each of which is incorporated by reference in its entirety). Microscopic cracks gradually formed and became larger as the oCVD PEDOT film was stretched further, interrupting the current conduction along the stretch direction. There were, however, complete conducting polymer pathways visible even at 150% extension. The dashed line in the far right image is to guide the eyes through a remaining continuous film path in the view window.

Example 5: Large Scale Application

The vapor-patterned oCVD PEDOT electrodes were used to monolithically fabricate large-area, series-integrated PV circuits directly on paper and glass. Each device layer was vapor-patterned by shadow masking to create anode-to-cathode

interconnections between the individual cells (Fig. 20). The J-V characteristics for 250 cell (0.1 x 0.3 cm²) circuits on paper and glass substrates show high open-circuit voltages of 50 V and 67 V, respectively (Fig. 12a), representing a near summation of voltages from all working cells in each series (minus losses from shorted devices).

Spatial distribution maps of individual solar cell performance in the series integrated circuit were recorded to gain insight about overall cell statistics and substrate morphological impacts. The cell voltage distributions on both glass and paper substrates (Fig. 12b) showed that PVs on each substrate achieve similar maxima (-0.4 V), with higher variance across the rougher paper circuit. Moreover, high(low) cell voltages are grouped spatially across the paper circuit, suggesting local differences in the substrate surface roughness and thus different levels of order in the thin-film device formation. The higher density of low open-circuit voltages on paper was likely a result of small shunt resistances in local areas of high roughness across the less-conformal, evaporated photoactive layers.

The light weight and foldability of these devices could provide an advantage in reducing the cost of their installations and opening new venues for application. The foldability of the paper PV circuits is shown in Fig. 12c, in which high voltages were produced in each folded three-dimensional configuration and were maintained during dynamic folding and unfolding. However, for final deployment these lightweight structures will require flexible thin film encapsulation to achieve sufficiently long lifetimes and provide other environmental protections (M. Jorgensen, K. Norrman, F. C. Krebs, Sol. Energy Mater. Sol. Cells 92, 686 (2008), which is incorporated by reference in its entirety).

Example 6: Device Encapsulation

Simple, passive, flexible thin-film encapsulation techniques can significantly improve cell lifetimes and can provide other unique protective benefits while maintaining the various papery qualities of the unpackaged circuits (Fig. 13). 250-cell series- integrated PV circuits on tracing paper were encapsulated on both sides with three encapsulants: 1) 5-mil thick plastic laminate applied with an office laminating machine, 2) 750-nm thick poly(monochloro-/?-xylylene) ("parylene-C") deposited by self-initiated CVD polymerization, and 3) 750-nm thick superhydrophobic poly(lH,lH,2H,2H- perfluorodecyl acrylate) ("PFDA") film deposited by initiated CVD (iCVD)

polymerization (see M. E. Alf et αΙ. , Αάν. Mater. 22, 1993 (2010), which is incorporated by reference in its entirety).

The packaged and unpackaged series-integrated circuits were then aged in air, accelerated by exposure to constant illumination (80 mW-cm^~2 halogen lamp) and elevated temperature (42 °C/108 °F) at open-circuit (Figs. 13a and 21). The power- efficiency/time trajectory showed that each thin- film encapsulant significantly improved lifetime over the unpackaged counterparts. The influence of ultrathin films on circuit lifetime was also evident in the unpackaged cells: removing the 10-nm thick layer of BCP more than doubled the rate of power decay. We emphasize that this lifetime test was performed on the full series-integrated circuits and thus approaches a lower limit on power lifetime, since the photocurrent of the full circuit was limited by that of the worst- performing cell in the series. The longest lifetime observed here, over 500 hours, compared favorably with other reports of shorter illuminated lifetime (see, e.g., X. Xi et al, Sol. Energy Mater. Sol. Cells 94, 924; and K. Kawano et al , Sol. Energy Mater. Sol. Cells 90, 3520 (2006), each of which is incorporated by reference in its entirety), similar "shelf lifetime of hybrid-encapsulated cells (W. J. Potscavage, S. Yoo, B. Domercq, B. Kippelen, Appl. Phys. Lett. 90 (2007), which is incorporated by reference in its entirety), and similar illuminated lifetime for an encapsulated single tandem cell (R. Franke, B. Maennig, A. Petrich, M. Pfeiffer, Sol. Energy Mater. Sol. Cells 92, 732 (2008), which is incorporated by reference in its entirety). With specific engineering and more sophisticated encapsulation techniques (such as, for example, active desiccants, multilayers, etc.) these dynamics should be readily extendable.

Packaging can also add specific functionalities to the paper circuits. For example, a laminated paper circuit (128 series-integrated cells) powered an LCD clock and related circuitry in air using ambient light from the window (Fig. 13b) while retaining high flexibility and providing a mechanical barrier to physical handling (Fig. 22). The submicron iCVD-coated circuit was foldable and also superhydrophobic, withstanding extended exposure to water droplets and even complete water submersion without shorting or exhibiting significant changes in performance (Fig. 13c). This paper PV circuit was also resilient to subsequent laser-jet printing, where the whole cell was fed through a roll-to-roll printer, while still maintaining efficiencies sufficient to power the LCD clock (Fig. 13d).

Other embodiments are within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A light absorbing or emitting device comprising: a substrate with a textured surface; and a conductive polymer coating on a surface of the substrate.

2. The light absorbing or emitting device of claim 1, wherein the textured surface porous or fibrous.

3. The light absorbing or emitting device of claim 1 or 2, wherein the substrate is flexible.

4. The light absorbing or emitting device of any one of claims 1-3, wherein the polymer coating is conformal to the surface of the substrate.

5. The light absorbing or emitting device of any one of claims 1-4, wherein the substrate is paper or cloth.

6. The light absorbing or emitting device of any one of claims 1-5, wherein the polymer coating includes monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles or optionally substituted anilines.

7. The light absorbing or emitting device of claim 6, wherein the polymer coating includes poly(3 ,4-ethylenedioxythiophene).

8. The light absorbing or emitting device of any one of claims 1-7, wherein the polymer coating includes at least one dopant.

9. The light absorbing or emitting device of any one of claims 1-8, further

comprising: an electrode; and an energy converting region capable of converting energy between photoenergy and electric energy.

10. The light absorbing or emitting device of claim 9, wherein the polymer coating an anode and the electrode is a cathode.

11. The light absorbing or emitting device of claim 9 or 10, wherein the energy converting region includes copper phthalocyanine, fullerene-C6o or bathocuprine.

12. The light absorbing or emitting device of any one of claims 9-11, wherein the energy converting region includes poly(p-phenylene vinylene), polyfluorene, poly(fluorenylene ethynylene), poly(phenylene ethynylene), polyfluorene vinylene, or polythiophene.

13. The light absorbing or emitting device of any one of claims 9-12, wherein the energy converting region includes at least one material selected from the group consisting of: silicon, copper indium diselenide, zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium oxide, magnesium sulfide, magnesium selenide, magnesium telluride, mercuric oxide, mercuric sulfide, mercuric selenide, mercuric telluride, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, or lead telluride.

14. The light absorbing or emitting device of any one of claims 9-13, further

comprising an encapsulant encapsulating the device.

15. The light absorbing or emitting device of claim 14, wherein the encapsulant is waterproof.

16. The light absorbing or light emitting device of any one of claims 1-15, wherein the device is a photovoltaic.

17. The light absorbing or light emitting device of any one of claims 1-16, wherein the device is a light emitting diode.

18. A light absorbing device comprising: a plastic substrate; and a conductive polymer coating on a surface of the substrate.

19. The light absorbing device of claim 18, wherein the substrate is flexible.

20. The light absorbing device of claim 18 or 19, wherein the surface of the substrate includes a plurality of functional groups.

21. The light absorbing device of claim 20, wherein the conductive polymer interacts with the plurality of functional groups.

22. The light absorbing device of claim 20 or 21, wherein the conductive polymer forms a covalent bond with the plurality of functional groups.

23. The light absorbing device of any one of claims 18-22, wherein the polymer coating includes monomeric units derived from optionally substituted thiophenes, optionally substituted pyrroles or optionally substituted anilines.

24. The light absorbing device of claim 23, wherein the polymer coating includes poly(3 ,4-ethylenedioxythiophene) .

25. The light absorbing device of any one of claims 18-24, wherein the polymer coating includes at least one dopant.

26. The light absorbing device of any one of claims 18-25, further comprising: an electrode; and an energy converting region capable of converting energy between photoenergy and electric energy.

27. The light absorbing device of claim 26, wherein the polymer coating is an anode and the electrode is a cathode.

28. The light absorbing device of claim 26 or 27, wherein the energy converting region includes copper phthalocyanine, fullerene-C6o or bathocuprine.

29. The light absorbing device of any one of claims 26-28, wherein the energy

converting region includes poly(p-phenylene vinylene), polyfluorene, poly(fluorenylene ethynylene), poly(phenylene ethynylene), polyfluorene vinylene, or polythiophene.

30. The light absorbing device of any one of claims 26-29, wherein the energy converting region includes at least one material selected from the group consisting of: silicon, copper indium diselenide, zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium oxide, magnesium sulfide, magnesium selenide, magnesium telluride, mercuric oxide, mercuric sulfide, mercuric selenide, mercuric telluride, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, or lead telluride.

31. The light absorbing device of any one of claims 18-30, wherein the device is a photovoltaic.

32. The light absorbing device of any one of claims 18-31, further comprising an encapsulant encapsulating the device.

33. The light absorbing device of claim 32, wherein the encapsulant is waterproof.

34. A light absorbing or emitting device comprising a plurality of individual light absorbing or emitting device elements arranged on a substrate with a textured surface, wherein each device element includes a conductive polymer coating on a surface of the substrate.

35. A method of making a light absorbing or light emitting device comprising:

providing a plastic or textured substrate including a conductive polymer on a surface of the substrate; and

depositing an energy converting region capable of converting energy between photoenergy and electric energy on the substrate.

36. A method of making a light absorbing or light emitting device comprising:

providing a plastic or textured substrate;

depositing a conductive polymer on a surface of the substrate in a first predetermined pattern;

depositing an energy converting region capable of converting energy between photoenergy and electric energy over the conductive polymer in a second predetermined pattern; and

depositing an electrode material over the energy converting region in a third predetermined pattern.

37. The method of claim 36, wherein the first predetermined pattern, the second

predetermined pattern, and the third predetermined pattern are selected together so as to form a plurality of individual device elements.

38. The method of claim 37, wherein the plurality of individual device elements are electrically connected.

39. The method of claim 37 or 38, wherein the plurality of individual device elements are connected in series.

40. The method of claim 37 or 38, wherein the plurality of individual device elements are connected in parallel.

41. The method of claims 37 or 38, wherein the plurality of individual device

elements are connected in a combination of series and parallel connections.

42. The method of any one of claims 36-41, further comprising encapsulating the device.

43. The method of claim 42, wherein encapsulating the device includes vapor

deposition.

44. The method of any one of claims 36-43, wherein depositing a conductive polymer on a surface of the substrate in a first predetermined pattern includes vapor deposition and the first predetermined pattern is defined by a first mask.

45. The method of claim 44, wherein depositing an energy converting region capable of converting energy between photoenergy and electric energy over the conductive polymer in a second predetermined pattern includes vapor deposition and the second predetermined pattern is defined by a second mask.

46. The method of claim 45, wherein depositing an electrode material over the energy converting region in a third predetermined pattern includes vapor deposition and the third predetermined pattern is defined by a third mask.

47. The method of any one of claims 36-46, wherein the energy converting region includes two or more layers of materials.