Crystalline and amorphous forms of silicon are the principal materials used for solid-state electronics and photovoltaics technologies. Silicon is therefore a well-studied material, although new structures and properties are still being discovered. Compression of bulk silicon, which is tetrahedrally coordinated at atmospheric pressure, results in a transition to octahedrally coordinated metallic phases. In compressed nanocrystalline Si particles, the initial diamond structure persists to higher pressure than for bulk material, before transforming to high-density crystals. Here we report compression experiments on films of porous Si, which contains nanometre-sized domains of diamond-structured material. At pressures larger than 10 GPa we observed pressure-induced amorphization. Furthermore, we find from Raman spectroscopy measurements that the high-density amorphous form obtained by this process transforms to low-density amorphous silicon upon decompression. This amorphous-amorphous transition is remarkably similar to that reported previously for water, which suggests an underlying transition between a high-density and a low-density liquid phase in supercooled Si (refs 10, 14, 15). The Si melting temperature decreases with increasing pressure, and the crystalline semiconductor melts to a metallic liquid with average coordination approximately 5 (ref. 16).

We combine small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with aerodynamic levitation techniques to study in situ phase transitions in the liquid state under contactless conditions. At very high temperatures, yttria-alumina melts show a first-order transition, previously inferred from phase separation in quenched glasses. We show how the transition coincides with a narrow and reversible maximum in SAXS indicative of liquid unmixing on the nanoscale, combined with an abrupt realignment in WAXS features related to reversible shifts in polyhedral packing on the atomic scale. We also observed a rotary action in the suspended supercooled drop driven by repetitive transitions (a polyamorphic rotor) from which the reversible changes in molar volume (1.2 +/- 0.2 cubic centimeters) and entropy (19 +/- 4 joules mole(-1) kelvin(-1)) can be estimated.