Electronic strengthening mechanism of covalent Si via excess electron/hole doping

Brittle fracture of a covalent material is ultimately governed by the strength of the electronic bonds. Recently, attempts have been made to alter the mechanical properties including fracture strength by excess electron/hole doping. However, the underlying mechanics/mechanism of how these doped electrons/holes interact with the bond and changes its strength is yet to be revealed. Here, we perform first-principles density-functional theory calculations to clarify the effect of excess electrons/holes on the bonding strength of covalent Si. We demonstrate that the bond strength of Si decreases or increases monotonically in correspondence with the doping concentration. Surprisingly, change to the extent of 30–40% at the maximum feasible doping concentration could be observed. Furthermore, we demonstrated that the change in the covalent bond strength is determined by the bonding/antibonding state of the doped excess electrons/holes. In summary, this work explains the electronic strengthening mechanism of covalent Si from a quantum mechanical point of view and provides valuable insights into the electronic-level design of strength in covalent materials.