Double glassy states and large spontaneous and conventional exchange bias in La1.5Ca0.5CoFeO6ferrimagnetic double perovskite.

The structural and magnetic properties of hole doped double perovskite La1.5Ca0.5CoFeO6have been investigated by measuring x-ray photoemission spectroscopy, neutron powder diffraction and magnetization. A ferrimagnetic transition is observed atTC∼ 167 K. The presence of anti-site disorder (ASD) in La1.5Ca0.5CoFeO6has also been demonstrated. Double re-entrant cluster glass transitions (T1∼ 11 K andTS∼ 35 K) were observed which has been attributed to the ASD effect. The presence of both large spontaneous exchange biasHSEB∼ 2.106 kOe and giant conventional exchange biasHCEB∼ 1.56 T at 5 K has also been observed which can be attributed to the coexistence of long range magnetic ordering and glassy state. The experimental observations were explained with the results obtained by the density functional theory calculation. The presence of double glassy states, large exchange-bias effect and different magnetic phases make this system a potential candidate for spintronic applications.

Understanding the correlation between orbital degree of freedom, lattice-striction and magneto-dielectric coupling in ferrimagnetic Mn1.5Cr1.5O4.

Dielectric anomaly observed in cubic Mn1.5Cr1.5O4around ferrimagnetic ordering temperature (TN) suggests a possible magneto-dielectric coupling in the system. This report confirms the presence of a weak but significant magneto-dielectric coupling in the system. Theab initiocalculations show a band gap of around 1.2 eV, with Fermi-level closer to the conduction band. The major features of conduction band nearest to the Fermi-level correspond todxzandd3z2-r2orbitals of Mn3+ion. Temperature-dependent neutron diffraction results show a rapid decay in structural parameters (lattice-striction and transition metal-oxygen bond length) aroundTN.We confirmed that these changes in structural parameters atTNare not related to structural transition but the consequences of orbital-ordering of Mn3+. The rapid decay in transition metal-oxygen bond length under internal magnetism of the system shows that magnetism could certainly manipulate the electric dipole moment and hence the dielectric constant of the system. Magneto-striction acts as a link between magnetic and dielectric properties.

Hydrophobic functionalization of cellulosic substrate by tetrafluoroethane dielectric barrier discharge plasma at atmospheric pressure.

Hydrophobic functionalization of cellulosic fabric (viscose) was carried out using helium/tetrafluoroethane (He/TFE) plasma, a commercially available fluorocarbon gas, at the atmospheric pressure. By selecting suitable plasma parameters, He/TFE plasma was produced and maintained in glow state so that the various fragments of TFE in plasma zone could react covalently with the cellulose. After the plasma treatment, the highly hydrophilic cellulosic fabric turned into superhydrophobic fabric with a water absorbency time of >> 60 min, a water contact angle of 153° and a water rolling angle of 5°. The functionalization was found to be wash durable to 25 laundry cycles. From the analyses of species present in plasma zone by optical emission spectroscopy (OES), gas-chromatography-mass spectrometry (GC-MS), and the chemical nature of the functionalized substrate by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS), a possible mechanism involved in the reaction of TFE fragments with cellulose macromolecule was arrived at. Further, it could be inferred that the modification took place only at the surface of the fibres at the nanometre level. The study postulates that it is possible to elucidate reactions undergoing in plasma zone and to control them to achieve desirable modification of substrates.

Extraordinary magnetic properties of double perovskite Eu2CoMnO6 wide band gap semiconductor.

Some novel magnetic behaviours in double perovskite Eu2CoMnO6 (ECMO) have been reported. The x-ray photoemission spectroscopy study shows the presence of mixed valence states of transition metal ions. The UV-visible absorption spectroscopic study suggests that the ECMO has a direct wide band gap. A second-order magnetic phase transition as a sudden jump in the magnetization curve has been observed around 124.5 K. The large bifurcation between the zero field cooling and field cooling, suggests existence of strong spin frustration in the system. The inverse DC susceptibility confirms the presence of the Griffiths like phase. Sharp steps in magnetization have been observed in the M-H curve at 2 K, which vanishes on increasing temperature. The AC susceptibility study demonstrates the Hopkinson like effect as well as the presence of volume spin-glass-like behaviour. The temperature dependent Raman spectrum shows the presence of spin-phonon coupling.

Probing the Griffiths like phase, unconventional dual glassy states, giant exchange bias effects and its correlation with its electronic structure in Pr2-x Sr x CoMnO6.

Crystal, electronic structure, dc and ac magnetization properties of the hole substituted (Sr2+) and partially B-site disordered double perovskite Pr2-x Sr x CoMnO6 system have been investigated. The XRD pattern analysis showed a systematic decrease in the lattice parameters owing to the enhanced oxidation states of the Co/Mn ions. The electronic structure study by XPS measurements suggested the presence of mixed valence states of the B-site ions (Co2+ /Co3+ and Mn3+ /Mn4+) with significant enhancement of the average oxidation states due to hole doping. The mere absence of electronic states near the Fermi level in the valence band (VB) spectra for both pure (x = 0.0) and Sr doped (x = 0.5) systems indicated the insulating nature of the samples. Sr substitution is observed to increase the spectral weight near the Fermi level suggesting for an enhanced conductivity of the hole doped system. The dc magnetization data divulged a Griffiths like phase above the long-range ordering temperature. A typical re-entrant spin glass like phase driven by the inherent anti-site disorder (ASD) has been recognized by ac susceptibility study for both the pure and doped systems. Most interestingly, the emergence of a new cluster glass like phase (immediately below the magnetic ordering temperature and above the spin-glass transition temperature) solely driven by the Sr substitution has been unravelled by ac magnetization dynamics study. Observation of these dual glassy states in a single system is scarce and hence placed the present system amongst the rare materials. The isothermal magnetization measurements further probed the exhibition of the giant exchange bias effect originated from the interfacial exchange interactions due to existence of low temperature antiferromagnetic clusters embedded in the glassy matrix.

Investigation of multi-mode spin-phonon coupling and local B-site disorder in Pr2CoFeO6 by Raman spectroscopy and correlation with its electronic structure by XPS and XAS studies.

Electronic structure of Pr2CoFeO6 (at 300 K) was investigated by x-ray photoemission spectroscopy (XPS) and x-ray absorption spectroscopy techniques. All three cations, i.e. Pr, Co and Fe were found to be trivalent in nature. XPS valance band analysis suggested the system to be insulating in nature. The analysis suggested that Co3+ ions exist in low spin state in the system. Moreover, Raman spectroscopy study indicated the random distribution of the B-site ions (Co/Fe) triggered by same charge states. In temperature-dependent Raman study, the relative heights of the two observed phonon modes exhibited anomalous behaviour near magnetic transition temperature T N ~ 270 K, thus indicating towards interplay between spin and phonon degrees of freedom in the system. Furthermore, clear anomalous softening was observed below T N which confirmed the existence of strong spin-phonon coupling occurring for at least two phonon modes of the system. The line width analysis of the phonon modes essentially ruled out the role of magnetostriction effect in the observed phonon anomaly. The investigation of the lattice parameter variation across T N (obtained from the temperature-dependent neutron diffraction measurements) further confirmed the existence of the spin-phonon coupling.

Local symmetry breaking in SnO2 nanocrystals with cobalt doping and its effect on optical properties.

X-ray photoemission spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) have been used to study the structural and morphological characteristics of cobalt doped tin(iv) oxide (Sn1-xCoxO2; 0 ≤ x ≤ 0.04) nanocrystals synthesized by a chemical co-precipitation technique. Electronic structure analysis using X-ray photoemission spectroscopy (XPS) shows the formation of tin interstitials (Sni) and reduction of oxygen vacancies (VO) in the host lattice on Co doping and that the doped Co exists in mixed valence states of +2 and +3. Using XRD, the preferential position of the Sni and doped Co in the unit cell of the nanocrystals have been estimated. Rietveld refinement of XRD data shows that samples are of single phase and variation of lattice constants follows Vegard's law. XRD and TEM measurements show that the crystallite size of the nanocrystals decrease with increase in Co doping concentration. SAED patterns confirm the monocrystalline nature of the samples. The study of the lattice dynamics using Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy shows the existence of many disorder activated forbidden optical phonon modes, along with the corresponding classical modes, signifying Co induced local symmetry breaking in the nanocrystals. UV-Vis spectroscopy shows that the optical band gap has red shifted with increase in doping concentration. The study of Urbach energy confirms the increase in disorder in the nanocrystals with Co doping. Local symmetry breaking induced UV emission along with violet, blue and green luminescence has been observed from the PL study. The spectral contribution of UV emission decreases and green luminescence increases with increase in doping. Using PL, in conjunction with Raman spectroscopy, the type of oxygen vacancy induced in the nanocrystals on Co doping has been confirmed and the position of the defect levels in the forbidden zone (w.r.t. the optical band gap) has been studied.

Valence State of Eu and Superconductivity in Se-Substituted EuSr2Bi2S4F4 and Eu2SrBi2S4F4.

Recently, we reported the synthesis and investigations of EuSr2Bi2S4F4 and Eu2SrBi2S4F4. We have now been able to induce superconductivity in EuSr2Bi2S4F4 by Se substitution at the S site (isovalent substitution) with Tc = 2.9 K in EuSr2Bi2S2Se2F4. The other compound, Eu2SrBi2S4F4, shows a significant enhancement of Tc. In Se-substituted Eu2SrBi2S4-xSexF4, we find Tc = 2.6 K for x = 1.5 and Tc = 2.8 K for x = 2, whereas Tc = 0.4 K in the Se-free sample. In addition to superconductivity, an important effect associated with Se substitution is that it gives rise to remarkable changes in the Eu valence. Our 151Eu Mössbauer and X-ray photoemission spectroscopic measurements show that Se substitution in both of the compounds Eu2SrBi2S4F4 and EuSr2Bi2S4F4 gives rise to an increase in the Eu2+ component in the mixed-valence state of Eu.

Pr2FeCrO6: A Type I Multiferroic.

We synthesized double perovskite Pr2FeCrO6 by solid-state method. Analysis of its X-ray powder diffraction shows that the compound crystallizes in a centrosymmetric structure with space group Pbnm. Our X-ray photoelectron spectroscopy (XPS) studies show that all the cations are present in +3 oxidation state. Magnetization studies of Pr2FeCrO6 show that the material is paramagnetic at room temperature and undergoes a magnetic transition below TCM = 250 K. We observe clear magnetic hysteresis loop, for example, below 150 K. A low remnant magnetization Mr, ∼0.05 µB/f. u., is inferred from the observed magnetic hysteresis loop. 57Fe Mössbauer study at 25 K shows a high hyperfine magnetic field of ∼53 T at the Fe nucleus, which corresponds to a magnetic moment of ∼6-7 µB/Fe. These two results together suggest a ferrimagnetic (nearly compensated or canted) ordering of the Fe moments. Mössbauer studies close to the ferrimagnetic ordering temperature suggest interesting magnetic relaxation effects. A dielectric anomaly observed at TCE = 453 K signals a ferroelectric ↔ paraelectric phase transition. We observe at room temperature a clear and well-defined ferroelectric hysteresis loop, PS = 1.04 µC/cm2, establishing ferroelectricity in the material. From these results, we conclude that Pr2FeCrO6 is a type I multiferroic (TCE > TCM).

Unusual Mixed Valence of Eu in Two Materials-EuSr2Bi2S4F4 and Eu2SrBi2S4F4: Mössbauer and X-ray Photoemission Spectroscopy Investigations.

We have synthesized two new Eu-based compounds, EuSr2Bi2S4F4 and Eu2SrBi2S4F4, which are derivatives of Eu3Bi2S4F4, an intrinsic superconductor with Tc = 1.5 K. They belong to a tetragonal structure (SG: I4/mmm, Z = 2), similar to the parent compound Eu3Bi2S4F4. Our structural and 151Eu Mössbauer spectroscopy studies show that, in EuSr2Bi2S4F4, Eu-atoms exclusively occupy the crystallographic 2a-sites. In Eu2SrBi2S4F4, 2a-sites are fully occupied by Eu-atoms and the other half of Eu-atoms and Sr-atoms together fully occupy 4e-sites in a statistical distribution. In both compounds Eu atoms occupying the crystallographic 2a-sites are in a homogeneous mixed valent state ∼2.6-2.7. From our magnetization studies in an applied H ≤ 9 T, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift toward 2+. Our XPS studies corroborate the occurrence of valence fluctuations of Eu and after Ar-ion sputtering show evidence of enhanced population of Eu2+-states. Resistivity measurements, down to 2 K, suggest a semimetallic nature for both compounds.

Structural, transport and optical properties of (La0.6Pr0.4)0.65Ca0.35MnO3 nanocrystals: a wide band-gap magnetic semiconductor.

(La0.6Pr0.4)0.65Ca0.35MnO3 system has been synthesized via a sol-gel route at different sintering temperatures. Structural, transport and optical measurements have been carried out to investigate (La0.6Pr0.4)0.65Ca0.35MnO3 nanoparticles. Raman spectra show that Jahn-Teller distortion has been decreased due to the presence of Ca and Pr in A-site. Magnetic measurements provide a Curie temperature around 200 K and saturation magnetization (MS) of about 3.43µB/Mn at 5 K. X-ray photoemission spectroscopy study suggests that Mn exists in a dual oxidation state (Mn(3+) and Mn(4+)). Resistivity measurements suggest that charge-ordered states of Mn(3+) and Mn(4+), which might be influenced by the presence of Pr, have enhanced insulating behavior in (La0.6Pr0.4)0.65Ca0.35MnO3. Band gap estimated from UV-Vis spectroscopy measurements comes in the range of wide band gap semiconductors (∼3.5 eV); this makes (La0.6Pr0.4)0.65Ca0.35MnO3 a potential candidate for device application.

Highly conductive poly(3,4-ethylenedioxypyrrole) and poly(3,4-ethylenedioxythiophene) enwrapped Sb2S3 nanorods for flexible supercapacitors.

Composites of poly(3,4-ethylenedioxypyrrole) or PEDOP and poly(3,4-ethylenedioxythiophene) or PEDOT enwrapped Sb2S3 nanorods have been synthesized for the first time for use as supercapacitor electrodes. Hydrothermally synthesized Sb2S3 nanorods, several microns in length and 50-150 nm wide, offer high surface area and serve as a scaffold for coating conducting polymers, and are a viable alternative to carbon nanostructures. Fibrillar morphologies are achieved for the PEDOP-Sb2S3 and PEDOT-Sb2S3 films in contrast to the regular granular topologies attained for the neat polymers. The remarkably high nanoscale (∼5 S cm(-1)) conductivity of the Sb2S3 nanorods enables facile electron transport in the composites. We constructed asymmetric supercapacitors using the neat polymer or composite and graphite as electrodes. High specific capacitances of 1008 F g(-1) and 830 F g(-1) (at 1 A g(-1)), enhanced power densities (504 and 415 W kg(-1)) and excellent cycling stability (88 and 85% capacitance retention at the end of 1000 cycles) are delivered by the PEDOP-Sb2S3 and PEDOT-Sb2S3 cells relative to the neat polymer cells. A demonstration of a light emitting diode illumination using a light-weight, flexible, supercapacitor fabricated with PEDOP-Sb2S3 and carbon-fiber cloth shows the applicability of Sb2S3 enwrapped conducting polymers as sustainable electrodes for ultra-thin supercapacitors.

Electrophoretically deposited reduced graphene oxide platform for food toxin detection.

Reduced graphene oxide (RGO) due to its excellent electrochemical properties and large surface area, has recently aroused much interest for electrochemical biosensing application. Here, the chemically active RGO has been synthesized and deposited onto an indium tin oxide (ITO) coated glass substrate by the electrophoretic deposition technique. This novel platform has been utilized for covalent attachment of the monoclonal antibodies of aflatoxin B1 (anti-AFB1) for food toxin (AFB1) detection. The electron microscopy, X-ray diffraction, and UV-visible studies reveal successful synthesis of reduced graphene oxide while the XPS and FTIR studies suggest its carboxylic functionalized nature. The electrochemical sensing results of the anti-AFB1/RGO/ITO based immunoelectrode obtained as a function of aflatoxin concentration show high sensitivity (68 µA ng(-1) mL cm(-2)) and improved detection limit (0.12 ng mL(-1)). The association constant (ka) for antigen-antibody interaction obtained as 5 × 10(-4) ng mL(-1) indicates high affinity of antibodies toward the antigen (AFB1).

Revelation of graphene-Au for direct write deposition and characterization.

Graphene nanosheets were prepared using a modified Hummer's method, and Au-graphene nanocomposites were fabricated by in situ reduction of a gold salt. The as-produced graphene was characterized by X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy (HR-TEM). In particular, the HR-TEM demonstrated the layered crystallites of graphene with fringe spacing of about 0.32 nm in individual sheets and the ultrafine facetted structure of about 20 to 50 nm of Au particles in graphene composite. Scanning helium ion microscopy (HIM) technique was employed to demonstrate direct write deposition on graphene by lettering with gaps down to 7 nm within the chamber of the microscope. Bare graphene and graphene-gold nanocomposites were further characterized in terms of their composition and optical and electrical properties.

Charge transport and electrochemical response of poly(3,4-ethylenedioxypyrrole) films improved by noble-metal nanoparticles.

Charge-transport phenomena and redox switching of poly(3,4-ethylenedioxypyrrole) (PEDOP) films embedded with Au and Ag nanoparticles have been investigated. In the bulk, charge transport can be described by an ohmic regime at low voltages and a space-charge-limited current regime at high voltages in PEDOP-Au, which is in contrast to trap-filled domains deduced for neat PEDOP and PEDOP-Ag nanocomposites, all indicating transitions driven by an external bias. This also allowed a direct estimation of a fairly high charge-carrier mobility at room temperature in PEDOP-Au, in addition to a higher donor density, which are advantageous for device applications. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy affirmed the prevalence of Au/Ag nanoparticles as nonleachable entities in PEDOP, thus allowing the movement of electrons through the conducting nanoaparticles during electrochemical switching, an effect that is absent in the neat PEDOP film. Valence-band spectra and optical studies revealed that nanoparticles narrowed the band gap and increased the absorption coefficient of PEDOP, which enhanced the electrochromic switching ability of PEDOP. A coloration efficiency enhancement by an order of magnitude, higher electrochemical charge intercalation capacity, and higher diffusion rates reflect the role of noble-metal nanoparticles in improving the conduction and electrochemical activity of PEDOP.

Red to blue high electrochromic contrast and rapid switching poly(3,4-ethylenedioxypyrrole)-Au/Ag nanocomposite devices for smart windows.

Poly(3,4-ethylenedioxypyrrole) (PEDOP)-Ag and PEDOP-Au nanocomposite films have been synthesized for the first time by electropolymerization of the conducting-polymer precursor in a waterproof ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, followed by Ag/Au nanoparticle incorporation. That the Ag/Au nanoparticles are not adventitious entities in the film is confirmed by a) X-ray photoelectron spectroscopy, which provides evidence of Ag/Au-PEDOP interactions through chemical shifts of the Ag/Au core levels and new signals due to Ag-N(H) and Au-N(H) components, and b) electron microscopy, which reveals Au nanoparticles with a face-centered-cubic crystalline structure associated with the amorphous polymer. Spectroelectrochemistry of electrochromic devices based on PEDOP-Au show a large coloring efficiency (η(max) =270 cm(2) C(-1), λ=458 nm) in the visible region, for an orange/red to blue reversible transition, followed by a second, remarkably high η(max) of 490 cm(2) C(-1) (λ=1000 nm) in the near-infrared region as compared to the much lower values achieved for the neat PEDOP analogue. Electrochemical impedance spectroscopy studies reveal that the metal nanoparticles lower charge-transfer resistance and facilitate ion intercalation-deintercalation, which manifests in enhanced performance characteristics. In addition, significantly faster color-bleach kinetics (five times of that of neat PEDOP!) and a larger electrochemical ion insertion capacity unambiguously demonstrate the potential such conducting-polymer nanocomposites have for smart window applications.

Poly(3,4-ethylenedioxythiophene)-ionic liquid functionalized graphene/reduced graphene oxide nanostructures: improved conduction and electrochromism.

Nanocomposite assemblies of poly(3,4-ethylenedioxythiophene) (PEDOT), embedded with (a) fluoro alkyl phosphate based ionic liquid functionalized graphene (ILFG) and (b) reduced graphene oxide (RGO) prepared from a modified Hummers' method, have been synthesized. Defect free graphene nanosheets within the size of a few nanometers were achieved in the PEDOT-ILFG nanocomposite. In contrast, structures comprising graphene oxide wrinkles interspersed with the amorphous polymer were obtained in the PEDOT-RGO nanocomposite. X-ray photoelectron spectroscopy showed that neat ILFG was considerably less oxidized as compared to the neat RGO, which ratified the superiority of the ionic liquid functionalization strategy over the conventional chemical approach, for exfoliating graphite. Substantially higher electrochemical activity, improved ionic/electronic conductivity, much faster switching rates, and an almost ballistic enhancement in the electrochromic coloration efficiency attained for the PEDOT-ILFG nanocomposite in comparison to PEDOT-RGO film were irrefutable proofs that demonstrated the ability of the ionic liquid to not only fortify the structure of graphene but also facilitate charge transport through the bulk of the film, by providing less impeded pathways. Since PEDOT-ILFG/-RGO nanocomposites of good uniformity have been achieved, this, to some extent, addresses the challenge associated with the processing of graphene based high performance materials for practical applications.

A dual electrochrome of poly-(3,4-ethylenedioxythiophene) doped by N,N'-bis(3-sulfonatopropyl)-4-4'-bipyridinium--redox chemistry and electrochromism in flexible devices.

An electrochromic zwitterionic viologen, N,N'-bis(3-sulfonatopropyl)-4-4'-bipyridinium, has been used for the first time for doping poly (3,4-ethylenedioxythiopene) (PEDOT) films during electropolymerization. Slow and fast diffusional rates for the monomer at deposition potentials of +1.2 and +1.8 V, respectively yielded the viologen-doped PEDOT films with granular morphology and with dendrite-like shapes. The dual electrochrome formed at +1.8 V, showed enhanced coloration efficiency, larger electrochemical charge storage capacity, and superior redox activity in comparison to its analogue grown at +1.2 V, thus demonstrating the role of dendritic shapes in amplifying electrochromism. Flexible electrochromic devices fabricated with the viologen-doped PEDOT film grown at +1.8 V and Prussian blue with an ionic liquid-based gel electrolyte film showed reversible coloration between pale and dark purple with maximum coloration efficiency of 187 cm2C(-1) at lambda=693 nm. The diffusional impedance parameters and switching kinetics of the device showed the suitability of this dual electrochrome formed as a single layer for practical electrochromic cells.

Investigation of confinement effects in ZnO quantum dots.

We report a simple method for the synthesis of Na(+) doped and stable zinc oxide quantum dots, using the quantum confinement atom method. An intense broad green photoluminescence (PL) was observed with a maximum located at approximately 535 nm when excited by UV radiation of 332 nm. The PL peak intensity is found to be highly dependent on the size of the quantum dots (QDs). Electron microscopy observation revealed that the radius of the QD was approximately 1 nm, which clearly indicated that the QDs are in the strong quantum confinement region (exciton Bohr radius, r(B), for bulk ZnO is 1.8 nm). Phase purity of ZnO and the presence of Na(+) was confirmed by x-ray diffraction (XRD) and atomic absorption spectroscopy (AAS), respectively. The results are well incremented by x-ray photoelectron spectroscopy (XPS) studies. Intentional ageing of QDs for several days under controlled experimental conditions such as temperature, relative humidity and pH etc, facilitated the formation of various nanostructures with a slight red shift in the PL peak position. Time resolved emission spectroscopy measurements indicated that PL decay time changes from 35 ns for QDs to 1660 micros for nanocrystals. The observed high-intensity and stable green PL emissions have been analyzed and thoroughly discussed.

Poly(3,4-ethylenedioxythiophene)-multiwalled carbon nanotube composite films: structure-directed amplified electrochromic response and improved redox activity.

Composite thin films of poly(3,4-ethylenedioxythiophene) (PEDOT)-enwrapped functionalized multiwalled carbon nanotubes (MWCNTs) have been synthesized over multiple length scales by electropolymerization of the monomer without the use of any other supporting electrolyte. The functionalized MWCNTs are incorporated into the positively charged polymer deposit as counterions during oxidative electropolymerization. The morphology, electrochemistry, and electrochromism of the PEDOT-MWCNT films have been compared with those of control PEDOT films doped by triflate ions. Such a comparison enabled us to demonstrate the profound effect of MWCNTs as counterions, realized in terms of better electropolymerization rate, higher conductivity, faster color-bleach kinetics, higher charge storage capacity, and substantially amplified coloration efficiency (eta = 414 cm(2) C(-1), lambda(max) = 575 nm, E = -1.5 V) in comparison to the values of eta reported to date for PEDOT. The strong interaction between the polymer and MWCNTs, the interconnected nanotubular structures, and the porous framework of the film allow facile charge transport and larger ion uptake during redox switching. Electrochemical investigations on devices based on PEDOT-MWCNT and control PEDOT films established the practical utility of PEDOT-MWCNT films as they show lower charge-transfer resistance, higher diffusional capacitance, and a much smaller amplitude of impedance as compared to control PEDOT films.