Over the last two decades, it has
been demonstrated that size effects have significant consequences
for the atomic arrangements and phase behavior of matter under extreme
pressure. Furthermore, it has been shown that an understanding of
how size affects critical pressure–temperature conditions provides
vital guidance in the search for materials with novel properties.
Here, we report on the remarkable behavior of small (under ∼5
nm) matrix-free Ge nanoparticles under hydrostatic compression that
is drastically different from both larger nanoparticles and bulk Ge.
We discover that the application of pressure drives surface-induced
amorphization leading to Ge–Ge bond overcompression and eventually
to a polyamorphic semiconductor-to-metal transformation. A combination
of spectroscopic techniques together with ab initio simulations were
employed to reveal the details of the transformation mechanism into
a new high density phaseamorphous metallic Ge.
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