Manufacturing multifunctional nanocomposite materials and engineered surface nanopatterns involves a strategic blend of topography, crystal structures, and chemistry. Here, we report the controllable formation of crystalline nanoparticles and intermetallic compounds on thin films of metallic glasses (Zr50Cu50, Ti50Cu50, and Zr67Ag33) irradiated by ultrafast laser beams. Mapping the structural modification of the photoexcited and subsequently heated alloys reveals previously neglected chemical reactions with air, offering a direct solution for incorporating nanoparticles into an amorphous oxide matrix and broadening the range of laser-induced surface self-organization features. Our findings are attributed to the occurrence and enrichment of oxygen surface contamination that reacts with selected elements of the metallic glasses. Additionally, the growth of the crystalline phase from undercooled liquid may originate from the dissolution of oxides. Finally, our results establish that the combination of crystalline nanoparticles on amorphous periodic patterns can be universally obtained in a wide range of binary systems of irradiated metallic glasses.

We present an effective approach for fabricating nanowell arrays in a one-step laser process with promising applications for the storage and detection of chemical or biological elements. Biocompatible thin films of metallic glasses are manufactured with a selected composition of Zr65Cu35, known to exhibit remarkable mechanical properties and glass forming ability. Dense nanowell arrays spontaneously form in the ultrafast laser irradiation spot with dimensions down to 20 nm. The flared shape observed by transmission electron microscopy is ideal to ensure chemical or biological material immobilization into the nanowells. This also indicates that the localization of the cavitation-induced nanopores can be tuned by the density and size of the initial nanometric interstice from the columnar structure of films deposited by magnetron sputtering. In addition to the topographic functionalization, the laser-irradiated amorphous material exhibits structural changes analyzed by spectroscopic techniques at the nanoscale such as energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy. Results reveal structural changes consisting of nanocrystals of monoclinic zirconia that grow within the amorphous matrix. The mechanism is driven by local oxidation process catalyzed by extreme temperature and pressure conditions estimated by an atomistic simulation of the laser-induced nanowell formation.

Surface nanostructuring by femtosecond laser is an efficient way to manipulate surface topography, creating advanced functionalities of irradiated materials. Thin-film metallic glasses obtained by physical vapor deposition exhibit microstructures free from grain boundaries, crystallites and dislocations but also characterized by a nanometric surface roughness. These singular properties make them more resilient to other metals to form laser-induced nanopatterns. Here we investigate the morphological response of Zr65Cu35 alloys under ultrafast irradiation with multipulse feedback. We experimentally demonstrate that the initial columnar microstructure affects the surface topography evolution and conditions the required energy dose to reach desired structures in the nanoscale domain. Double pulses femtosecond laser irradiation is also shown to be an efficient strategy to force materials to form uniform nanostructures even when their thermomechanical properties have a poor predisposition to generate them.