Laterally controlled template electrodeposition of polyaniline

Abstract Polyaniline (PANi) was electrodeposited in gold‐coated nanoporous alumina membranes (NAMs) by anodic polymerization of aniline. PANi deposition was followed by cathodic deposition of Ag or Cu, to form a layer of PANi–metal segmented nanowires in the NAM. The compact PANi nanowires fill the entire pore volume, providing a sharp transition from the polymer to the metal segment. The deposited metal layer enables SEM visualization of the PANi nanowire length in the membrane. Deposition of Cu on PANi nanowires occurs at potentials where the PANi is in its reduced leucoemeraldine state, with no evidence for penetration of the metal into the polymer matrix. The mechanism of metal ion reduction on the nonconducting polymer wires is not yet clear. Free‐standing segmented PANi–Ag and PANi–Cu nanowires obtained by membrane dissolution show a sharp heterojunction between the polymer and metal phases and are mechanically stable. Aniline electropolymerization in the insulating NAM under a lateral potential gradient generated a thickness gradient of the PANi deposit, revealed by subsequent Cu deposition. The potential‐dependent length of the PANi nanowires follows the PANi conductivity pattern, reaching a maximum in the region of stability of the conducting emeraldine phase. The results demonstrate the possibility of obtaining nonlinear graded materials using electrochemical systems showing a complex current–voltage behavior.