Reactive sputtering onto an ionic liquid, a new synthesis route for bismuth-based nanoparticles

Metallic bismuth and Bi-oxyfluoride nanoparticles (NPs) are successfully synthesized by non-reactive and reactive sputtering of a Bi target onto 1-butyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide ([BMIM][TFSI]) ionic liquid (IL). Non-reactive sputtering is realized in pure Ar plasma, where isotropic, well crystallized and dispersed Bi NPs of 3-7 nm are obtained. The diameter and the size distribution of these NPs do not significantly vary with the power, gas pressure, and sputtering time; but these sputtering parameters seem to influence the NP concentration. Then, the introduction of O₂ and CF₄ gases in addition to Ar enables the reaction of radicals from plasma with Bi clusters at the liquid's top surface to form Bi-oxyfluoride NPs of 3-12 nm in diameter with photocatalytic activity. Hence, the reactive sputtering onto an IL is an efficient, original and promising method for synthesizing Bi-based compound NPs. Finally, we propose a mechanism based on reactions of species from plasma at the IL surface to explain the formation of Bi-compounds by reactive sputtering.