Processes for fabricating multi- and monolayer silicene on catalyst metal surfaces by means of plasma-enhanced chemical vapor deposition (PECVD). Silicene is grown by means of PECVD from a starting mixture of H2 and SiH4 having an H2:SiH4 ratio of 100 to 400 on an Ag(111) substrate having a substrate temperature between 20° C. and 290° C., with the deposition being performed for about 10-25 minutes at an RF power between 10 W and 500 W and under a chamber pressure between about 100 mTorr and 1300 mTorr. In most cases, the substrate will be in the form of an Ag(111) film sputtered on a fused silica substrate. A multi-layer silicene film can be formed by extending the deposition time past 25 minutes.