Colloidally synthesized free-standing Ge qdots with a unique core–shell structure were demonstrated to be a viable bio-imaging probe.

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 phaseamorphous metallic Ge.