Crystalline and amorphous forms of silicon are the principal materials used
for solid-state electronics and photovoltaics technologies. Silicon is the
refore a well-studied material, although new structures and properties are
still being discovered(1-4). Compression of bulk silicon, which is tetrahed
rally coordinated at atmospheric pressure, results in a transition to octah
edrally coordinated metallic phases(5). In compressed nanocrystalline Si pa
rticles, the initial diamond structure persists to higher pressure than for
bulk material, before transforming to high-density crystals(6). Here we re
port compression experiments on films of porous Si, which contains nanometr
e-sized domains of diamond-structured material(7-9). At pressures larger th
an 10 GPa we observed pressure-induced amorphization(10,11). Furthermore, w
e rnd from Raman spectroscopy measurements that the high-density amorphous
form obtained by this process transforms to low-density amorphous silicon u
pon decompression. This amorphous-amorphous transition is remarkably simila
r to that reported previously for water(12,13), which suggests an underlyin
g transition between a high-density and a low-density liquid phase in super
cooled Si (refs 10, 14, 15). The Si melting temperature decreases with incr
easing pressure, and the crystalline semiconductor melts to a metallic liqu
id with average coordination similar to5 (ref. 16).