Self-Detachment of Nanoporous Thin Films

Abstract

Nanoporous metals consist of a network of interconnected ligaments with diameters tunable between 5 and 500 nm. The talk focusses on nanoporous metal thin films prepared by electrochemical dealloying of 300 nm thick Au25Ag75 films deposited on a pure Au base layer. This type of nanoporous gold film is the subject of many studies investigating the material as sensor, as catalyst, or as substrate for energy storage.The massive Au base layer is intended as an adhesion promoter and to prevent the corrosion from attacking the substrate. Yet, contrary to expectation, we observed that the as-dealloyed nanoporous films developed a gap near the base layer, with extremely loose connection. Screening electron micrographs in earlier publications revealed that the deficit in connectivity is ubiquitous – even though it has not been broached. We could readily reproduce the feature in kinetic Monte Carlo simulations of dealloying, with no special assumptions on the processes near the base layer. The talk will describe these observations, and we argue that the evolution of the connectivity in nanoporous thin films is sensitive to gradients, in the direction of the film thickness, of the laterally averaged surface mean curvature. Specifically, surface diffusion driven by the energetically favorable planar substrate results in a net current from ligaments connected to the substrate towards the substrate, leading to degradation and eventual pinch-off of these ligaments. A similar phenomenon occurs at the outer surface, causing densification and retraction of the outermost ligaments.Our findings suggest that this phenomenon may be relevant for all nanoscopic contact interfaces where surface diffusion is sufficiently fast. These results have significant implications for the design and implementation of nanoporous thin films in various applications, including sensor and actuator devices. Mitigation strategies will be discussed.Reference:G. Henkelmann, D. Waldow, M. Liu, L. Lührs, Y. Li and J. Weissmüller; Self-Detachment and Subsurface Densification of Dealloyed Nanoporous Thin Films. Nano Lett 22 (2022) 6787. Figure 1