Transient absorption studies on 3,6-dibromo polyvinylcarbazole and its model compounds

3,6-Dibromo-N-ethylcarbazole (DBNEC) and its polymeric analogue poly-3,6-dibromovinylcarbazole (PDBVCz) were studied by transient absorption spectroscopy. The transient absorption spectrum of the 3,6-dibromo-N-ethylcarbazole radical cation and decay rate constants of radical cations of 3,6-dibromo-N-ethylcarbazole and its polymeric analogue are presented. In the case of unsubstituted carbazole, the ratio of the yield of radical cation of monomer to polymer is 2.0, whereas in the case of PDBVCz, under the same experimental conditions, the yield of the radical cation is an order of magnitude less in comparison with the monomer model compound DBNEC. This drastic difference in yield has been correlated to the difference in the conformational structure of the polymer as evidenced by nuclear magnetic resonance spectroscopy. (C) 1997 Elsevier Science S.A.

Electrocatalytic oxidation of C-3-aliphatic alcohols on electrodeposited Pd-PEDOT nanodendrites in Alkaline medium

Nanodendritic Pd is electrodeposited on poly(3,4-ethylenedioxythiophene) (PEDOT) coated carbon paper electrode. Electrodeposited Pd is non-dendritic in the absence of PEDOT. The electrooxidation of C-3-aliphatic alcohols, namely, propanol (PA), 1,2- propanediol (1, 2-PD), 1, 3-propanediol (1, 3-PD), and glycerol (GL) is studied in 1.0 M NaOH. The catalytic activity of nanodendritic Pd is greater than that of non-dendritic Pd for oxidation of the four alcohols molecules. Among those molecules the oxidation rate increases as: PA< 1, 2-PD < 1, 3-PD < GL. The cyclic voltammetric oxidation current peak appearing in the reverse direction of the sweep is greatly influenced by the nature of alcohol. The reduction of oxide film on Pd surface is attributed to affect the magnitude of backward peak current density. The amperometry and repeated cyclic voltammetry data suggest a high stability of nanodendritic Pd in alkaline medium. Glycerol is expected to be an appropriate alcohol for application as a fuel in alkaline fuel cells at nanodendritic electrodeposited Pd.

Charge transport in transparent conductors: A comparison

A comparative investigation of charge transport properties is presented, for polymeric [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)], single-wall carbon nanotube (SWNT) and inorganic (indium tin oxide, ITO), transparent conducting electrodes. The polymeric and nanotube systems show hopping transport at low temperatures, in contrast with the disordered-metal transport in ITO. The low temperature magnetotransport (up to 11 T) and high electric-field transport (up to 500 V/cm) indicate the significant role of nanoscopic scale disorder for charge transport in polymer and nanotube based systems. The results show that characteristic length scales like localization length correlates with the nanomorphology in these systems. Further, the high frequency conductivity measurements (up to 30 MHz) in PEDOT:PSS and SWNT follow the extended pair approximation model [σ(ω)=σ(0)[1+(ω/ω0)s].

Electrochromic, magnetotransport and AC transport properties of vapor phase polymerized PEDOT(VPP PEDOT)

Poly(3,4-ethylenedioxy)thiophene (PEDOT) doped with tosylate ion (PEDOT-tosylate or VPP PEDOT) was synthesized by vapor phase polymerization (VPP) technique on glass as well as on glass/ITO and the electrochromic properties were investigated. Compared with that of PEDOT-PSS spin-coated on glass/ITO, the studies showed that VPP PEDOT has a lower work function and better electrochromic properties. The magneto and AC transport properties studies were done on VPP PEDOT coated on glass substrate. The system shows 2-dimensional variable range hopping and wave function shrinkage of charge carriers.

PEDOT-PSSA as an alternative support for Pt electrodes in PEFCs

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulphonic acid) (PSSA) supported platinum (Pt) electrodes for application in polymer electrolyte fuel cells (PEFCs) are reported. PEDOT-PSSA support helps Pt particles to be uniformly distributed on to the electrodes, and facilitates mixed electronic and ionic (H+-ion) conduction within the catalyst, ameliorating Pt utilization. The inherent proton conductivity of PEDOT-PSSA composite also helps reducing Nation content in PEFC electrodes. During prolonged operation of PEFCs, Pt electrodes supported onto PEDOT-PSSA composite exhibit lower corrosion in relation to Pt electrodes supported onto commercially available Vulcan XC-72R carbon. Physical properties of PEDOT-PSSA composite have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. PEFCs with PEDOT-PSSA-supported Pt catalyst electrodes offer a peak power-density of 810 mW cm(-2) at a load current-density of 1800 mA cm(-2) with Nation content as low as 5 wt.% in the catalyst layer. Accordingly, the present study provides a novel alternative support for platinized PEFC electrodes.

PEDOT-PSSA as an alternative support for Pt electrodes in PEFCs

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulphonic acid) (PSSA) supported platinum (Pt) electrodes for application in polymer electrolyte fuel cells (PEFCs) are reported. PEDOT-PSSA support helps Pt particles to be uniformly distributed on to the electrodes, and facilitates mixed electronic and ionic (H+-ion) conduction within the catalyst, ameliorating Pt utilization. The inherent proton conductivity of PEDOT-PSSA composite also helps reducing Nation content in PEFC electrodes. During prolonged operation of PEFCs, Pt electrodes supported onto PEDOT-PSSA composite exhibit lower corrosion in relation to Pt electrodes supported onto commercially available Vulcan XC-72R carbon. Physical properties of PEDOT-PSSA composite have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. PEFCs with PEDOT-PSSA-supported Pt catalyst electrodes offer a peak power-density of 810 mW cm(-2) at a load current-density of 1800 mA cm(-2) with Nation content as low as 5 wt.% in the catalyst layer. Accordingly, the present study provides a novel alternative support for platinized PEFC electrodes

Electrical and optical characterization of conducting polymers by THz time-domain spectroscopy

The absorption and index of refraction of polypyrrole (PPy) and poly-3-methylthiophene (PMeT), from low frequencies up to 4 THz, have been measured by tera-Herz (THz) time-domain spectroscopy. The complex conductance was obtained over this range of frequency. Highly conducting metallic samples follow the Drude model, whereas less conducting ones fit the localization-modified Drude model. The carrier scattering time and mobility in conducting polymers can be directly determined from these measurements.

Electrooxidation of formic acid at platinum nanoclusters electrodeposited on PEDOT coated carbon paper electrode

Nanoclusters of Pt were electrochemically deposited on a conducting polymer, namely, poly(3,4-ethylenedioxythiophene) (PEDOT), which was also electrochemically deposited on carbon paper current collector. PEDOT facilitated uniform distribution of Pt nanoclusters, when compared with Pt electrodeposition on bare carbon paper substrate. Spectroscopy data indicated absence of any interaction between PEDOT and Pt. The electrochemically active surface area as measured from carbon monoxide adsorption followed by its oxidation was several times greater for Pt-PEDOT/C electrode in comparison with Pt/C electrode. The catalytic activity of Pt-PEDOT/C electrode for electrooxidation of formic acid was significantly greater than that of Pt/C electrode. Amperometry data suggested that the electrodes were stable for continuous oxidation of HCOOH.

Novel thiophene derivative hybrid composite solar cells

In this work composites of poly(3-hexylethiophene) (P3HT) and a thiophene derivative (7, 9-di (thiophen-2-yl)-8H-cyclopenta[a]acenaphthylen-8-one) (DTCPA) having donor acceptor architecture (DAD) were prepared. Photovoltaic properties of these hybrid composites were evaluated. DTCPA, which is a highly crystalline organic molecule with wide absorption range, was observed to improve the open circuit voltage of the solar cell. Furthermore, DTCPA crystals acts as a nucleating center and increases the molecular ordering of P3HT in the composite. Improved charge separation efficiency was observed by photoluminescence spectroscopy. Because of high built in potential in these devices, large open circuit voltage was observed. (C) 2011 Elsevier B.V. All rights reserved.

Tunable device properties of free-standing inorganic/organic flexible hybrid structures obtained by exfoliation

We report the fabrication of free-standing flexible inorganic/organic hybrid structures by exfoliating ZnO nanostructured films from the flat indium tin oxide (ITO)/silicon/sapphire substrates using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). Strong interaction between ZnO and PEDOT: PSS and the thermomechanical response of PEDOT: PSS are the key issues for the exfoliation to prevail. The performance of the free-standing hybrid structures as rectifiers and photodetectors is better as compared to ITO supported hybrid structures. It is also shown that device properties of hybrid structures can be tuned by using different electrode materials. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729550]

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Durability of Pt/C and Pt/MC-PEDOT catalysts under simulated start-stop cycles in polymer electrolyte fuel cells

A composite of mesoporous carbon (MC) with poly(3,4-ethylenedioxythiophene) (PEDOT) is studied as catalyst support for platinum nanoparticles. The durability of commercial Pt/carbon and Pt/MC-PEDOT as cathode catalyst is investigated by invoking air-fuel boundary at the anode side so as to foster carbon corrosion at the cathode side of a polymer electrolyte fuel cell (PEFC). Pt/MC-PEDOT shows higher resistance to carbon corrosion in relation to Pt/C. Electrochemical techniques such as cyclic voltammetry (CV) and impedance measurements are used to evaluate the extent of degradation in the catalyst layer. It is surmised that the resistance of MC-PEDOT as catalyst support toward electrochemical oxidation makes Pt/MC-PEDOT a suitable and stable cathode catalyst for PEFCs.

Channel II photocurrent quantification in narrow optical gap polymer-fullerene solar cells with complimentary acceptor absorption

Most charge generation studies on organic solar cells focus on the conventional mode of photocurrent generation derived from light absorption in the electron donor component (so called channel I). In contrast, relatively little attention has been paid to the alternate generation pathway: light absorption in the electron acceptor followed by photo-induced hole transfer (channel II). By using the narrow optical gap polymer poly(3,6-dithieno3,2-b] thiophen-2-yl)-2,5-bis(2-octyldodecyl)-pyrrolo- 3,4-c]pyrrole-1,4-dione-5',5 `'-diyl-alt-4,8-bis(dodecyloxy) benzo1,2-b:4,5-b'] dithiophene-2,6-diyl with two complimentary fullerene absorbers; phenyl-C-61-butyric acid methyl ester, and phenyl-C-71-butyric acid methyl ester (70-PCBM), we have been able to quantify the photocurrent generated each of the mechanisms and find a significant fraction (>30%), which is derived in particular from 70-PCBM light absorption.

Non-Enzymatic Electroanalysis of Glucose on Electrodeposited Au-PEDOT Dendrites

Electrodeposition of Au on poly (3,4-ethylenedioxythiophene) (PEDOT) coated carbon paper electrode results in the formation of a stable 3-D urchin-like morphology. Au-PEDOT/C electrode exhibits higher surface area, greater catalytic activity, higher sensitivity and lower detection limit for glucose analysis in an alkaline medium than Au/C electrode. Au-PEDOT/C electrode exhibits a linear current response in glucose concentration ranging up to 10 mu M with sensitivity of 515 mu A cm(-2) mu M-1 (on the basis of geometric area) and a low detection limit of 0.03 mu M with signal to noise ratio of 3. Thus, the PEDOT under-layer improves the property of Au for glucose analysis. (c) 2013 The Electrochemical Society.