Electroless Dealloying of Thin-Film Nanocrystalline Au-Ag Alloys: Mechanisms of Ligament Nucleation and Sources of Its Synthesis Variability.

Control of ligament size in nanoporous gold through process inputs in chemical dealloying holds the potential to exploit its size dependent properties in applications in energy and biomedicine. While its morphology evolution is regulated by the kinetics of coarsening, recent studies are focused on the early stage of dealloying (e.g., ∼ 5-42 at. % in residual alloy content) to understand mechanisms of ligament nucleation and its role in altering process-structure relationships. This paper examines this stage in chemical dealloying of nanocrystalline Au 49 Ag 51 thin films and finds that ligaments are nucleated uniformly through its thickness due to the dealloying front rapidly propagating through the thickness of the film. Further, through the establishment of process-structure relationships with large data sets (i.e., 80 samples), this paper quantifies sources of variability that alter the kinetics of ligament growth such as aging of the precursor (e.g., grain growth) and solution evaporation. It is found that ligament diameter is better predicted by the residual silver content rather than by the dealloying time even amidst both effects and independent control of ligament diameter and solid area fraction is demonstrated within a limited window.