High Hole Doping Redirects Pressure-Induced Phase Transformation of Silicon

The pressure-induced phase transformation of semiconductors, particularly silicon (Si), has long been a fundamental problem in condensed matter physics. Decades of research have predominantly focused on external factors such as temperature, load, and unloading rate, leaving the role of inherent electronic properties fundamentally unresolved. This Letter addresses this gap by demonstrating that hole doping (i.e., hole concentration) is a critical governing factor in the pressure-induced phase transformation. We experimentally establish, for the first time, that high hole-doping redirects the phase transformation by facilitating the amorphization of Si. Our simulations powered by carrier-dependent interatomic potentials reveal that the three-coordinated Si atoms are dynamically stabilized by the localized holes during the decompression from β-tin (Si-II) phase, irreversibly driving the collapse of long-range order in Si to facilitate amorphization. Furthermore, we experimentally observe the hole-facilitated amorphization in Ge and SiC, while GaAs shows a somewhat weaker yet consistent trend. Our Letter unveils the hidden role of holes from mere charge carriers to fundamental mediators of structural stability under high pressure, establishing a new perspective on the interplay between electronic and structural properties in semiconductors.