Monoshaped and monosized copper nanostructured particles have been prepared by potentiostatic electrochemical deposition on an ultrathin polypyrrole (PPY) film, electrochemically grown on a Si(100) substrate sputter-coated with a thin gold film or gold-film electrode (GFE). The crystal size and the number density of the copper nanocrystals have been examined by varying several deposition parameters, including the thickness of the gold film, the PPY film thickness, the applied potential, and the Cu2+ and the electrolyte concentrations for copper deposition. Optimal conditions for uniform growth ofnanocrystals well-dispersed on the GFE have been determined, along with insight into the mechanism of crystal growth. A minimum gold film thickness of 80 nm is required to eliminate the effects of the gold-silicon interface. The PPY film thickness and homogeneity principally affect the shape uniformity of the nanocrystals, while the copper deposition potential could be used to regulate the size and number density of the nanocrystals. Both the Cu2+ and electrolyte concentrations are also found to play important roles in controlling the electrodeposition of nanocrystal growth.

Using X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), the room temperature (RT) adsorption and thermal evolution of monochlorobenzene (MCB) and 1,3-dichlorobenzene (1,3-DCB) on Si(100)2×1 have been investigated and compared with that of 1,2-dichlorobenzene (1,2-DCB) reported previously. Like 1,2-DCB, the C 1s features observed at 284.6 (C 1 ) and 286.0 eV (C 2 ) for both MCB and 1,3-DCB could be attributed to the C-H and C-Cl bonds, respectively. The C 1 /C 2 intensity ratios for MCB (5.0) and 1,3-DCB (2.0) are found to follow the stoichiometric ratios of the C-H to C-Cl bonds for MCB and 1,3-DCB, respectively, indicating that both MCB and 1,3-DCB adsorb on Si(100)2×1 molecularly with negligible C-Cl dissociation at RT, in marked contrast to the partial C-Cl dissociation found for 1,2-DCB. Unlike 1,2-DCB with two discernible Cl 2s features at 270.3 and 271.2 eV, a single Cl 2s feature at 271.2 eV is observed for MCB and 1,3-DCB, in accord with the single local chemical environment for Cl. The TPD results show that MCB undergoes molecular desorption exclusively, similar to that found for benzene. Both molecular desorption and recombinative HCl desorption are found for 1,3-DCB, similar to that for 1,2-DCB. Despite the different Cl contents and relative Cl locations on the benzene ring, both MCB and 1,3-DCB exhibit RT adsorption behavior remarkably similar to that of benzene. To explain the C-Cl dissociation observed for 1,2-DCB, we propose a possible transition state involving the Cl atoms located at more physically compatible positions with the surface Si dimers in order to facilitate the conversion of 1,2-DCB (preferentially over 1,3-DCB) to dissociated products at RT. However, the thermal evolution of 1,3-DCB is closer to that of 1,2-DCB than that of MCB and benzene. The breakage of C-Cl bonds is found to occur at a relatively low temperature of 425 K, which suggests a relatively low activation barrier for the dechlorination of 1,3-DCB adspecies. Calculated energetics for 1,4-DCB on Si(100)2×1 shows that double dechlorination is not as favorable a process as those for 1,2-DCB and 1,3-DCB.