Substrate interaction mediated control of phase separation in FIB milled Ag–Cu thin films

Nanofabrication is an integral part of the realization of advanced functional devices ranging from optical displays to memory devices. Focused-ion beam (FIB) milling is one of the most widely used nanofabrication methods. Conventionally, FIB milling has been carried out for patterning single-phase stable thin films. However, the influence of FIB milling on the phase separation of metastable alloy films during subsequent treatments has not been reported. Here, we show how FIB milling of Ag–Cu thin films influences the separation process and microstructure formation during post-milling annealing. The phase-separated microstructure of the film consists of fine, randomly distributed Ag-rich and Cu-rich domains, whereas adjacent to milled apertures (cylindrical holes), we observe two distinctly coarser rings. A combination of imaging and analysis techniques reveals Cu-rich islands dispersed in Ag-rich domains in the first ring next to the aperture, while the second ring constitutes mostly of Ag-rich grains. Copper silicide is observed to form in and around apertures through reaction with the Si-substrate. This substrate interaction, in addition to known variables like composition, temperature, and capillarity, appears to be a key element in drastically changing the local microstructure around apertures. Thus, the current study introduces new avenues to locally modulate the composition and microstructure through an appropriate choice of the film-substrate system. Such an ability can be exploited further to tune device functionalities for possible applications in plasmonics, catalysis, microelectronics, and magnetics.