Characterization and modeling of tungsten nanoparticles generated by laser-assisted chemical vapor deposition

Tungsten nanoparticles were generated by photolytical (UV) laser-activated chemical vapor deposition from WF6/H2/Ar gas mixture. Emission spectroscopy of thermal radiation allowed temperature determination of the nanoparticles while varying the laser fluence. A model including known cooling mechanisms was used to calculate the laser-induced temperature as a function of time and laser fluence, where the only fitting parameter was the absorption efficiency of the particles, obtained from measured temperatures. Size decrease of the particles due to evaporation was modeled at different laser fluences, and connected to size-distribution measurements from transmission electron microscopy micrographs, where a maximum geometric mean diameter (for the experimental conditions used) of 10 nm was observed at a laser fluence of ∼120 mJ/cm2. Measurements and the model calculations showed that the laser-excited particles reached the melting temperature of tungsten at ∼95 mJ/cm2. Above ∼130 mJ/cm2, very high rates of evaporation of W atoms were found, resulting in a decrease in size of the deposited particles. Crystalline, metastable β-W nanoparticles were found above ∼100 mJ/cm2 by both electron and x-ray diffraction. Below fluences of ∼100 mJ/cm2, i.e., corresponding to the value necessary for melting, amorphous nanoparticles were obtained