Thin films of guest-free type-II Si clathrate (Si-136) were fabricated on Si(111) wafers in two steps: NaxSi136 thin-film formation by thermal decomposition of NaSi precursor films and Na removal from the NaxSi136 film by a heat treatment with iodine. Cross-sectional TEM observation and XRD and Raman measurements verified the formation of 1-mu m-thick Si-136 films on the Si wafer. Since the prepared films showed n-type conduction, pn junction devices were developed by a Si136/p-type Si structure. This device showed a photovoltaic (PV) response under white light illumination. The thin film formation and the PV response of Si136 indicated this Si allotrope to be the next-generation platform for semiconductor technology. (C) 2016 Elsevier B.V. All rights reserved.