The thermal behavior of silicon nanoparticles (Si NPs) was investigated for the preparation of silicon thin film using a solution process. TEM analysis of Si NPs, synthesized by inductively coupled plasma, revealed that the micro-structure of the Si NPs was amorphous and that the Si NPs had melted and merged at a comparatively low temperature (~750 °C) considering bulk melting temperature of silicon (1414 °C). A silicon ink solution was prepared by dispersing amorphous Si NPs in propylene glycol (PG). It was then coated onto a silicon wafer and a quartz plate to form a thin film. These films were annealed in a vacuum or in an N₂ environment to increase their film density. N2 annealing at 800 °C and 1000 °C induced the crystallization of the amorphous thin film. An elemental analysis by the SIMS depth profile showed that N₂annealing at 1000 °C for 180 min drastically reduced the concentrations of carbon and oxygen inside the silicon thin film. These results indicate that silicon ink prepared using amorphous Si NPs in PG can serve as a proper means of preparing silicon thin film via solution process.