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Solution and refinement of the crystal structure of fac-Ir(ppy)(3) is severely hampered by systematic twinning and pseudo-symmetry.fac-Ir(ppy)(3) Crystallizes in the centrosymmetric space group P (3) over bar as has been deduced from single-crystal structure refinement and investigations of the second harmonic generation (SHG) of fac-Ir(ppy)(3) powder as compared to two standard materials. The topology of the molecular packing of fac-Ir(ppy)(3) is identical to the packing observed for [Ru(bpy)(3)](0), however, the site symmetry of all Ir(ppy)(3) molecules is necessarily lowered from D-3 to C-3. Packing motifs with intermolecular "pi-pi interactions" of T-shaped and "shifted pi stack" geometry are realized. The systematic twinning leads to the occurrence of crystalline domains with rigorously alternating chirality within the bulk of the domains but with homochiral fac-Ir(ppy)(3) contacts at the domain interfaces. These differences in packing motifs are displayed in the emission spectra and in the high-pressure-induced shifts of the emission. The emission maximum of the bulk material at 18 350 cm(-1) (545 nm) and of the domain interfaces at 19 700 cm-1 (507 nm) experience for p < 25 kbar and T = 295 K red shifts of Delta nu/Delta p = -(12 +/- 2) cm(-1)/kbar, and -(22 +/- 4) cm(- 1)/kbar, respectively
The differential approach is based on the determination of dimensionless differential slope, for instance, of current-voltage characteristics (IVC), I=f(V). This slope (a) is given by formula alpha=d(lgI)/d(lgV). With such definition the ranges of constancy of the a(V) dependency correspond to the part of IVC characterized by the power behaviour (I similar to V-alpha). The differential slope of alpha(V) dependency gamma = d(lg alpha)/dlgV determines the exponent behaviour of curve (I similar to exp {eV(y)/kT}). Processing by the differential approach of the investigated theoretical or experimental characteristics permits us to determine the peculiarity of charge flow mechanisms, temperature behaviour of conductivity, etc. The theoretical base and some applications of differential approach to the investigation of the current-voltage, temperature and degradation characteristics of the polyaniline and poly(p- phenilenevinilene) based structures have been shown. (c) 2005 Elsevier B.V. All rights reserved
Films of emeraldine base of polyaniline (PAni) doped by various transition metal salts have been prepared, and current-voltage characteristics of the indium-tin oxide (ITO)/PAni film/metal electrode heterostructures were investigated. It was found that the electrical characteristics of the heterostructures are greatly affected by the dopant used and the metal electrode used. Different dopants resulted in different current anomalies with asymmetric current-voltage characteristics. Depending on the dopant used, the exponential and power law of the current behavior can be distinguished. Depending on the metal electrode used, two different regimes of current passing have been found at low applied voltages, namely, a nearly ohmic regime for the indium electrode, and a diode regime for the aluminum electrode. The diode regime was found to accompany by a positive charge accumulation in the film near the film/metal interface, which creates a built-in potential in the film. The amount of positive charges accumulated at the interface and therefore the value of the built-in potential can be reversibly increased or reduced by successive runs of the applied voltage in the forward or reverse direction, respectively. (C) 2004 Elsevier B.V. All rights reserved