Dynamic quartz crystal impedance measurements of polyvinylferrocene film deposition

Dynamic crystal impedance measurements were used to study the electrochemically-driven deposition of polyvinylferrocene (PVF) films from dichloromethane solutions of PVF onto Au electrodes of a quartz crystal microbalance. Under all the conditions studied, the PVF films were non-rigid, to an extent that depended upon several experimental factors. Films deposited from solutions containing perchlorate salts of tetraalkylammonium salts departed less from rigidity than those deposited under otherwise identical conditions from tetrafluoroborate media. In contrast, the use of different tetraalkylammonium cations, or the use of a potential sweep vs, a potential step from 0 V to the deposition potential (0.7 V), made no significant difference. The departure from rigid characteristics varied with coverage. For the interval of time during deposition that the coverage was 10-160 nmol cm(-2) (of monomeric ferrocene units), the films showed no additional departure from rigidity. On the basis that the upper figure corresponds closely to a ''monolayer'' of terminally attached chains of mean length, we attribute this behaviour to the presence of a dense film, within which chain motion is considerably restrained.