Thin film of guest-free type-II silicon clathrate on Si(111) wafer

•Type II Si clathrate thin films are grown on Si wafers.•The Si clathrate-Si wafer boundary is observed by transmission electron microscopy.•A device prepared using the Si clathrate film shows photovoltaic response.

Thin films of guest-free type-II Si clathrate (Si136) 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-μm-thick Si136 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.