Dynamics of charge migration in poly(para-phenylene vinylene) films and nanocomposites with single walled carbon nanotubes.

We present in this paper a comprehensive study of the migration dynamics of the charges underlying transient photoluminescence (PL) processes in poly(para-phenylene vinylene) (PPV) samples from room temperature to 13 K. In order to interpret experimental data, we have modelled the long-time PL decays (from 100 to 1000 ps) using a time function proportional to [Formula: see text] in which the parameter α is evaluated in a Monte Carlo simulation on polymeric chains. The one dimensional chains (2000 sites long) are formed by random sequences of long and short conjugated segments whose bimodal distributions have been elaborated in previous works in order to reproduce the PL band shapes and peak positions. Intra-chain and inter-chain dynamics are taken into account in the migration of the photogenerated charges from short to long conjugated segments. The statistical analysis is performed by averaging over a total of 10(6) trials for each initial conditions. The values of α have been determined for pristine PPV films and PPV composite films with single-walled carbon nanotubes. This theoretical analysis is in good agreement with experimental data and provides a coherent description for the migration of the photogenerated charges in such inhomogeneous polymeric systems.

Electropolymerization of N-ethylcarbazole on single walled carbon nanotubes-cyclic voltammetry, raman and FTIR studies.

The electrochemical polymerization of N-ethyl carbazole (EK) on carbon nanotubes (CNs) films immersed in a LiClO4/acetonitrile solution was studied by cyclic voltammetry. Cyclic voltammograms recorded on a blank Pt electrode were compared with those obtained when CNs films were deposited on a Pt plate. In the latter case, the oxidation maximum is not clearly observed. Using the Raman scattering studies, oligomers of poly(N-ethyl carbazole) (PEK) on CNs are shown to be formed. A covalent functionalization of CNs with the PEK oligomers is demonstrated by FTIR spectroscopy studies. The formation of new C-C covalent bonds between CNs and the benzene ring of PEK induces steric hindrance effects that are shown in FTIR spectra by the increase in the intensity of the absorption band at 1072 cm(-1) attributed to the vibration of C-H in plane deformation of aromatic ring. The influence of the monomer and the supporting electrolyte concentration as well as the sweep rate on the polymerization conditions in the case of the composites based on the PEK oligomers and CNs were also investigated.

Surface enhanced Raman scattering studies on poly(3,4-ethylene dioxythiophene)/single-walled carbon nanotubes composites and their application to rechargeable lithium batteries.

In this paper, surface enhanced Raman scattering (SERS) studies on the chemical polymerization of 3,4-ethylene dioxythiophene (EDOT) in the presence of single-walled carbon nanotubes (SWNTs) are reported. Both a non-covalent and covalent functionalization of SWNTs with poly(3,4-ethylene dioxythiophene) (PEDOT) is invoked as a result of the following variations induced in the SERS spectra of PEDOT and SWNTs: (i) the appearance of a Raman line at 140 cm(-1) indicating the formation of a new covalent bond between PEDOT and SWNTs; (ii) an increase in the intensity of the Raman line at 705 cm(-1), associated with the deformation vibration mode of C-S-C bond, the result of a steric hindrance effect induced by the bonding of PEDOT on SWNTs; and (iii) the enhancement of the Raman band with maximum at 1540 cm(-1) (G- component) in SWNTs when the PEDOT weight in the PEDOT/SWNTs composite increases. Using the PEDOT/SWNTs composite as a positive electrode and an electrolytic solution containing LiPF6, the charge-discharge characteristics of the rechargeable lithium cells are determined. High specific discharge capacity are reported for the PEDOT/SWNTs composite (ca. 218 mAh g(-1)) in comparison with PEDOT doped with FeCl4- ions (ca. 25 mAh g(-1)).

Elaboration of conjugated polymer nanowires and nanotubes for tunable photoluminescence properties.

Prototypal photoluminescent nanofibres of poly-(p-phenylene-vinylene) (PPV) were prepared by the wetting template method in polycarbonate nanoporous membranes with an easy all-in solution polymer precursor route. Both nanowires and nanotubes were obtained by varying the dilution of the polymer precursor in methanol prior to thermal conversion. PPV nanotubes exhibit unique features, such as blue-shifted emission at 2.80 eV, higher quantum yield, and longer fluorescence lifetime with respect to PPV films. These effects are attributed to the cancellation of interchain interactions that are consistent with nanoscale tubular structures formed from weakly interacting and short polymer chain segments. The synthesis of these objects opens up perspectives for tunable photoluminescence properties in the blue spectral range and for biochemical applications.

Steady state and transient photoluminescence in poly-p-phenylene vinylene films and nanofibers.

We report in this paper experimental data on steady state and transient photoluminescence of poly-p-phenylene vinylene in the form of nanofibers prepared with a template method and converted at 110 degrees C. Results are compared to those obtained from films of different thicknesses converted at the same temperature. Data are analyzed by a model of bimodal distribution of conjugation lengths and the photoluminescence band shapes, evaluated in the framework of this model, are also presented.

Quantum well effect in bulk PbI(2) crystals revealed by the anisotropy of photoluminescence and Raman spectra.

On subjecting a bulk 2H-PbI(2) crystal to vacuum annealing at 500 K followed by a sudden cooling at liquid nitrogen temperature stacking faults are generated that separate distinct layers of nanometric thickness in which different numbers of I-Pb-I atomic layers are bundled together. Such structures, containing two, three, four, five etc I-Pb-I atomic layers, behave as quantum wells of different widths. The signature of such a transformation is given by a shift towards higher energies of the fundamental absorption edge, which is experimentally revealed by specific anisotropies in the photoluminescence and Raman spectra. The quantum confining effect is made visible by specific variations of a wide extra-excitonic band (G) at 2.06 eV that originates in the radiative recombination of carriers (electrons and holes), trapped on the surface defects. The excitation spectrum of the G band, with p polarized exciting light, reveals a fine structure comprised of narrow bands at 2.75, 2.64, 2.59 and 2.56 eV, which are associated with the PbI(2) quantum wells formed from two, three, four and five I-Pb-I atomic layers of 0.7 nm thickness. Regardless of the polarization state of the laser exciting light of 514.5 nm (2.41 eV), which is close to the band gap energy of PbI(2) (2.52 eV), the Raman scattering on bulk as-grown PbI(2) crystals has the character of a resonant process. For p polarized exciting light, the Raman scattering process on vacuum annealed PbI(2) becomes non-resonant. This originates from the quantum well structures generated inside the crystal, whose band gap energies are higher than the energy of the exciting light.

ZnO particles of wurtzite structure as a component in ZnO/carbon nanotube composite.

Composites based on carbon nanotubes and ZnO particles with needle shapes were prepared for applications in energy storage. Depending on the temperature (85 or 25 °C) at which the reaction between NaOH and ZnCl(2) was carried out, particles with two different morphologies: needle-shaped (NS) and double-pyramid-shaped (DPS), respectively, are obtained. Scanning electron microscopy, photoluminescence, UV-Vis absorption spectroscopy, x-ray diffraction and Raman light scattering studies reveal that the NS and DPS particles belong to ZnO with wurtzite (WZ) structure and ε-Zn (OH)(2) as precursors of ZnO, respectively. Using the ZnO/carbon nanotube composite as a negative electrode and an electrolytic solution containing LiPF(6), the charge-discharge characteristics of rechargeable lithium ions cells were determined. Additional information concerning the electrochemical reactions at the interface of the two electrodes was obtained by cyclic voltammetry.

Optical cooling of single-walled carbon nanotubes as revealed by their anti-Stokes Raman spectra.

Semiconducting single-walled carbon nanotubes resonantly excited by the interband E(22)(S) electronic transitions (at 1064 nm) display for the two components of the radial Raman band-one associated with the isolated tubes and the other associated with the bundled tubes-an anti-Stokes/Stokes Raman intensity ratio (I(aS)/I(S)) which deviates oppositely from the predictions of the Maxwell-Boltzmann formula. A cooling and heating vibration process, evidenced by an enhancement and diminishment of (I(aS)/I(S)), appears in the isolated and bundled nanotubes, respectively. Here we confirm a cooling process, observed only for semiconducting nanotubes, which emerges from the relaxation of the E(22)(S) excited state by the electronic relaxation from E(22)(S) to E(11)(S) that precedes the spontaneous luminescence emission at E(11)(S). Metallic nanotubes do not exhibit luminescence and no cooling effect is observed. Both semiconducting and metallic nanotubes show for the bundled component of the radial Raman band an enhancement of (I(aS)/I(S)) such as is frequently observed in a coherent anti-Stokes Raman scattering process.

Raman spectroscopy of single-wall boron nitride nanotubes.

Single-wall boron nitride nanotubes samples synthesized by laser vaporization of a hexagonal BN target under a nitrogen atmosphere are studied by UV and visible Raman spectroscopy. We show that resonant conditions are necessary for investigating phonon modes of BNNTs. Raman excitation in the UV (229 nm) provides preresonant conditions, allowing the identification of the A1 tangential mode at 1370 cm(-1). This is 5 cm(-1) higher than the E(2g) mode in bulk h-BN. Ab initio calculations show that the lower frequency of bulk h-BN with respect to large diameter nanotubes and the single sheet of h-BN is related to a softening of the sp2 bonds in the bulk due to interlayer interaction.

Evidence of temperature dependent charge migration on conjugated segments in poly-p-phenylene vinylene and single-walled carbon nanotubes composite films.

We present new results of temperature dependence of photoluminescence spectra carried out on poly-p-phenylene vinylene (PPV) and on PPV composite films with single-walled carbon nanotubes. By performing studies at different temperatures (87 and 300 K), we show that a distribution of conjugated PPV segments is needed to interpret experimental data. At the microscopic scale, such a distribution corresponds to the morphological picture of poorly packed short chain segments and well-packed ordered long chain segments. Within this scheme, a new interpretation emerges for explaining the specific behavior of the photoluminescence bands. In particular, the two most intense components of the photoluminescence spectra of PPV thermally converted at 300 degrees C (2.23 and 2.43 eV at 300 K) change drastically their relative intensity when the observation temperature decreases. This effect is interpreted as due to the inhibition of charge migration to longer segments and to radiative recombination occurring mainly on n = 5 conjugated segments.