EP2585543A2 - Polymère conducteur sur un substrat texturé ou en plastique - Google Patents

Polymère conducteur sur un substrat texturé ou en plastique

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Publication number
EP2585543A2
EP2585543A2 EP11736488.5A EP11736488A EP2585543A2 EP 2585543 A2 EP2585543 A2 EP 2585543A2 EP 11736488 A EP11736488 A EP 11736488A EP 2585543 A2 EP2585543 A2 EP 2585543A2
Authority
EP
European Patent Office
Prior art keywords
substrate
light absorbing
emitting device
paper
conductive polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11736488.5A
Other languages
German (de)
English (en)
Inventor
Karen K. Gleason
Vladimir Bulovic
Miles C. Barr
Jill A. Rowehl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Massachusetts Institute of Technology
Original Assignee
Massachusetts Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/822,691 external-priority patent/US9214639B2/en
Application filed by Massachusetts Institute of Technology filed Critical Massachusetts Institute of Technology
Publication of EP2585543A2 publication Critical patent/EP2585543A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/84—Parallel electrical configurations of multiple OLEDs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/86—Series electrical configurations of multiple OLEDs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to a conductive polymer coating a surface of a textured or plastic substrate.
  • 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.
  • LEDs light emitting diodes
  • PV photovoltaic
  • a conductive polymer coating can be deposited on a substrate that can include a textured surface.
  • Vs Versatile, substrate-independent, thin-film photovoltaics
  • ultra-lightweight substrates e.g., fiber-based papers; -0.001 g-cm "2 , and under 40 ⁇ in thickness
  • common PV substrates e.g., glass and plastic
  • 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).
  • oCVD oxidative chemical vapor deposition
  • 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.
  • the textured surface can be porous or fibrous.
  • 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.
  • 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.
  • 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,
  • 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, in
  • the device can further include an encapsulant encapsulating the device.
  • the encapsulant can be waterproof.
  • the light absorbing device can be a photovoltaic. In other embodiments, the light emitting device can be a light emitting diode.
  • a light absorbing device can include a plastic substrate and a conductive polymer coating on a surface of the substrate.
  • the substrate can be flexible.
  • 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.
  • 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.
  • the light absorbing device can further include an electrode and an energy converting region capable of converting energy between photoenergy and electric energy.
  • the polymer coating can be an anode and the electrode can be a cathode.
  • 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,
  • 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, in
  • the device can further include an encapsulant encapsulating the device.
  • the encapsulant can be waterproof.
  • the light absorbing device can be a photovoltaic.
  • a light absorbing or emitting device in another aspect, 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.
  • 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.
  • 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.
  • the energy converting region can include two or more layers of materials.
  • 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 SARANTM 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 SARANTM wrap as it is
  • Fig. 3d is a graph demonstrating the conductivity of an oCVD PEDOT electrode on newsprint after repeated folding.
  • 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
  • Fig. 7 shows a conductive polymer conforming to fibers of substrates.
  • 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. 10b 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. 10b is a schematic diagram of the oCVD process.
  • Fig. 10b is a photograph of a 200 nm-thick PEDOT film vapor
  • Fig. 11a is a schematic depiction of PV device architecture; C 6 o 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.
  • 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 cm 2 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
  • 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. 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. 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, SaranTM 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 SaranTM wrap ( ⁇ 10- ⁇ thick) after varying degrees of anisotropic stretching.
  • 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. 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 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.
  • conducting polymers deposited directly on substrates that are inexpensive, widely available, and compatible with high-throughput manufacturing.
  • 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.
  • PVs photovoltaics
  • LEDs light emitting diodes
  • 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.
  • PEDOT poly-3,4-ethylenedioxy-thiophene
  • 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
  • PEDOT polystyrene sulfonic acid
  • BAYTRON PTM polystyrene sulfonic acid
  • Bayer's BAYTRON P materials PEDOT stabilized with polystyrene sulfonate
  • NMP N- methyl-pyrolidone
  • BAYTRON P can also be suitable as a hole-injecting layer in LEDs and photo vol taics, increasing device efficiency by up to 50%.
  • Conducting polymer materials can be formed via oxidative polymerization of aniline, pyrrole, thiophene, or their derivatives.
  • 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:
  • 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.
  • inert electrode material 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.
  • 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
  • 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.
  • 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).
  • an oxidant for example, iron(III) chloride, iron(III) tosylate, hydrogen peroxide, potassium iodate, potassium chromate, ammonium sulfate, or tetrabutylammonium persulfate (TBAP).
  • 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
  • NOPF 6 dissolved nitrosonium hexafluorophosphate
  • 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.
  • Dipping a substrate material into a solution containing oxidants like FeCl 3 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.
  • Vacuum deposition of polyaniline films using evaporation can yield conductivities of about 10 "4 S/cm.
  • 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.
  • PECVD Plasma-enhanced chemical vapor deposition
  • aniline, thiophene or parylene-substituted precursors can be another method of depositing aniline, thiophene or parylene-substituted precursors.
  • 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.
  • Thermally activated hot-wire CVD can be used to polymerize aniline or vinyl- containing monomers, including phenylenevinylene or vinylcarbazole, but no
  • 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.
  • the monomer can undergo a ring-opening metathesis polymerization mechanism when contacted by the catalyst.
  • 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 FeCl 3 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.
  • PEDOT polystyrene sulfonic acid
  • BAYTRON PTM water soluble polyanion, polystyrene sulfonic acid
  • BAYTRON PTM polystyrene sulfonic acid
  • 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.
  • a method of making a conducting material can be a chemical vapor deposition (CVD) process that forms thin films of electrically active polymers.
  • CVD chemical vapor deposition
  • 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.
  • 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
  • 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.
  • 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
  • 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 NOPF 6 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.
  • the substrate can have a texture.
  • 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, TYVEKTM, 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.
  • 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 ⁇ , 1 ⁇ to 2 ⁇ , or 2 ⁇ to 3 ⁇ .
  • 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.
  • 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.
  • the deposited film then may be heated, sometimes under vacuum (e.g., 15 mmHg, 30 mmHg, or 45 mmHg), to remove unreacted monomer.
  • 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
  • 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).
  • 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.
  • 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.
  • rinsing the dried film in a solution of "dopant" ionic salts 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.
  • 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.
  • 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).
  • 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.
  • 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 ⁇ g/cm 2 , less than about 100 ⁇ g/cm 2 , less than about 50 ⁇ g/cm 2 , less than about 10 ⁇ g/cm 2 , or less than about 5 ⁇ g/cm 2 .
  • the required mass per surface area depends on the specific surface area of the substrate to be coated.
  • a smooth flat substrate, 1 cm 2 in area can require coverage of only 1 cm 2 of area and thus the specific surface area of 1 cm 2 /cm 2 .
  • a 1 cm 2 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 (cm 2 /cm 2 ) of the fabric and the density of the coating (g/cm 3 ) will yield the mass per surface area (g/cm 2 ).
  • the methods of making a conducting material can have several advantages.
  • 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.
  • in situ covalent bonding chemical grafting
  • Conducting polymers can be fabricated directly on ultra- lightweight "everyday” substrates, including as-purchased fiber-based papers (-0.001 g cm “2 , ⁇ 40- ⁇ 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 can have a surface area greater than area the substrate occupies.
  • 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 ⁇ , 1 ⁇ to 2 ⁇ , or 2 ⁇ to 3 ⁇ .
  • 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 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.
  • Substrates can have textured surfaces that require fabrication processes capable of conformally coating complex geometries.
  • the conductive polymer can be conformal to the substrate.
  • 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).
  • 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. 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.
  • 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 ⁇ g/cm 2 , less than about 100 ⁇ g/cm 2 , less than about 50 ⁇ g/cm 2 , less than about 10 ⁇ g/cm 2 , or less than about 5 ⁇ g/cm 2 .
  • the required mass per surface area depends on the specific surface area of the substrate to be coated.
  • a smooth flat substrate, 1 cm 2 in area can require coverage of only 1 cm 2 of area and thus the specific surface area of 1 cm 2 /cm 2 .
  • a 1 cm 2 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 (cm 2 /cm 2 ) of the fabric and the density of the coating (g/cm 3 ) will yield the mass per surface area (g/cm 2 ).
  • 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).
  • an organic sulfonic acid 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 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%.
  • flexing of commercially fabricated ITO-coated PET substrates decreased the film conductance over 400-fold due to formation of cracks (Fig. 15).
  • oCVD PEDOT on 10- ⁇ thick SaranTM wrap increased in conductivity under moderate stretching (25%) and maintained significant electrical conductance until substrate failure ( ⁇ 200% extension).
  • 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/C 60 /BCP/Ag. In particular, it can have the structure ITO (100 nm)/PEDOT:PSS (70 nm)/CuPc (20 nm)/C 60 (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.
  • 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.
  • 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.
  • 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 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.
  • 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
  • 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 ⁇ , 1 ⁇ to 2 ⁇ , or 2 ⁇ to 3 ⁇ .
  • 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 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.
  • Substrates can have textured surfaces that require fabrication processes capable of conformally coating complex geometries.
  • the conductive polymer can be conformal to the substrate.
  • 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).
  • 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 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 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 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 (cm 2 /cm 2 ) of the fabric and the density of the coating (g/cm 3 ) will yield the mass per surface area (g/cm 2 ).
  • 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).
  • 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 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.
  • a second electrode can be present in addition to the first electrode and the conductive polymer (Fig. 9c).
  • the second electrode can be located on the substrate.
  • the conductive polymer can replace a second electrode.
  • the electrode can be a cathode and the conductive polymer can be an anode.
  • 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
  • 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.
  • the energy converting region can convert photoenergy into electric energy.
  • 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.
  • 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,
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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,
  • 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.
  • 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
  • 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.
  • 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.
  • 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).
  • lamination film e.g., as used in offices for laminating paper
  • parylene-C parylene-C
  • PFDA poly(lH,lH,2H,2H-perfluorodecyl acrylate)
  • 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).
  • EDOT vapor-phase monomer
  • FeCls oxidant reactants
  • the printed polymer patterns (down to 20 ⁇ 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 conducting polymer layer can provide both low sheet resistance (3 ⁇ 4) and high optical transmittance (7) which are related by the following equation:
  • 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)
  • 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 SaranTM Premium Wrap (SC Johnson).
  • Stretch testing was performed using a MTS Nano Instruments Nano-UTM nanotensile tester. 5 mm x 1 mm oCVD PEDOT electrodes on SaranTM 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
  • 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.
  • Electrochemical testing took place in an aqueous 0.1 M solution of sulfuric acid (VWR).
  • VWR sulfuric acid
  • the CVD PEDOT film on ITO was the working electrode
  • platinized copper was the counter electrode
  • SCE saturated calomel electrode
  • 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.
  • 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).
  • 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).
  • 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.
  • 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).
  • 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).
  • 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)).
  • PS polystyrenes
  • PET polyethylene terephthalates
  • 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.
  • the flexibility of the oCVD electrode may have allowed the subsequent device layer to retain its integrity upon flexing.
  • oCVD film thickness was much less than the RMS surface roughness of the paper (-2-4 ⁇ ).
  • 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.
  • the thickness of the CuPc layer was increased from 20 nm to 100 nm.
  • Ultrathin paper substrates e.g., tissue paper
  • Fig. 4g shows a thin-film photovoltaic cell integrated into the wings of a paper airplane on a -50 cm 2 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 .
  • 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.
  • oCVD polymers can be similarly integrated in other large and small-area optoelectronic device structures.
  • 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.
  • the oCVD PEDOT was covalently bonded to SaranTM Wrap (a PET-based substrate), inhibiting slippage and ensuring that the polymer electrode was stretched along with the substrate.
  • SaranTM Wrap a PET-based substrate
  • 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).
  • 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
  • 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.
  • 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).
  • 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)
  • 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.
  • 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.
  • Packaging can also add specific functionalities to the paper circuits.
  • 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).

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Abstract

La présente invention concerne une substance conductrice qui peut comprendre un substrat texturé et un revêtement de polymère conducteur sur une surface du substrat. Le substrat peut être flexible (par exemple, du papier ou un plastique flexible) et les propriétés conductrices du matériau peuvent résister à la déformation du substrat. Des dispositifs résilients et flexibles peuvent être formés sur le substrat.
EP11736488.5A 2010-06-24 2011-06-24 Polymère conducteur sur un substrat texturé ou en plastique Withdrawn EP2585543A2 (fr)

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US9793479B2 (en) 2011-12-16 2017-10-17 Massachusetts Institute Of Technology Methods for fabricating devices including photovoltaic devices
US8896010B2 (en) 2012-01-24 2014-11-25 Cooledge Lighting Inc. Wafer-level flip chip device packages and related methods
US20130187540A1 (en) 2012-01-24 2013-07-25 Michael A. Tischler Discrete phosphor chips for light-emitting devices and related methods
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