pi-Conjugation and conformation in a semiconducting polymer: small angle x-ray scattering study

Small angle X-ray scattering (SAXS) in poly[2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution has shown the important role of pi-electron conjugation in controlling the chain conformation and assembly. By increasing the extent of conjugation from 30 to 100 %, the persistence length (l_p) increases from 20 to 66 Angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. Xylene enhances the rigidity of PPV backbone to yield extended structures, while tetrahydrofuran solvates the side groups to form compact coils in which the l_p is much shorter.Comment: accepted (J. Phy. Cond. Mat.

Correlated conformation and charge transport in multiwall carbon nanotube - conducting polymer nanocomposites

The strikingly different charge transport behaviors in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylene dioxythiophene - polystyrene sulfonic acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small angle X-ray scattering (SAXS). The SAXS studies indicate assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following 1D-VRH is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (~ 5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity (TCR) is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube - polymer boundary resulting in large delocalization.Comment: Accepted J. Phys.: Condens. Matte

Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions

Small angle X-ray scattering (SAXS) studies of poly2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) with varying conjugation, and polyethylene dioxythiophene complexed with polystyrene sulfonate (PEDOT-PSS) in different solvents have shown the importance of the role of pi-electron conjugation and solvent-chain interactions in controlling the chain conformation and assembly. In MEH-PPV, by increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in the fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. In the case of PEDOT-PSS, the chains undergo solvent induced expansion and enhanced chain organization. The clusters formed by chains are better correlated in dimethyl sulfoxide (DMSO) solution than water, as observed in the scattered intensity profiles. The values of radius of gyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtained from the unified scattering function (Beaucage) analysis, give evidence for chain expansion from compact (in water) to an extended coil in DMSO solutions, which is consistent with the Kratky plot analysis. The mechanism of this transition and the increase in dc conductivity of PEDOT-PSS in DMSO solution are discussed. The onset frequency for the increase in ac conduction, as well as its temperature dependence, probes the extent of the connectivity in the PEDOT-PSS system. The enhanced charge transport in PEDOT-PSS in DMSO is attributed to the extended chain conformation, as observed in the SAXS results

Variations in Magnetic Properties of Nanostructured Nickel

The magnetic properties of carbon nanotube encapsulated nickel nanowires (C. E. nanowires of diameter similar to 10 nm), and its comparison to other forms of Ni are carried out in this work. The saturation magnetization (M-s) and coercivity (H-c) for C. E. nanowires are 1.0 emu/g and 230 Oe. The temperature dependence of coercivity follows T-0.77 dependence indicating a superparamagnetic behavior. The field-cooled and zero-field-cooled plots indicate that the blocking temperature (T-B) similar to 300 K. These altered magnetic properties of C. E. nanowires are mainly due to the nanoscale confinement effect from carbon nanotube encapsulation. The shape and magnetic environment enhance the total magnetic anisotropy of C. E. nanowires by a factor of four