First-Principles Dissociation Pathways of BCl3 on the Si(100)‑2 × 1 Surface

BCl3 is a promising acceptor precursor for atomic-precision δ-doping of silicon, as it has been observed to rapidly dissociate into boron doped into the silicon surface and surface chlorine, which can be removed upon annealing. The chemical pathway and the resulting kinetics, through which BCl3 adsorbs and dissociates on silicon, however, have only been partially explained. In this work, we use density functional theory to expand the dissociation reactions of BCl3 to include reactions that take place across multiple silicon dimer rows and reactions which end in a bare B atom either at the surface, substituted for a surface silicon, or in a subsurface position. We further simulate the resulting scanning tunneling microscopy images for each of these BClx dissociation fragments, demonstrating that they often display distinct features that may allow for relatively confident experimental identification. Finally, we input the full dissociation pathway for BCl3 into a kinetic Monte Carlo model, which simulates realistic reaction pathways as a function of environmental conditions, such as the pressure and temperature of dosing. We find that BCl2 is broadly dominant at low temperatures, while high temperatures and ample space on the silicon surface for dissociation encourage the formation of bridging BCl fragments and B substitutions on the surface. This work provides the chemical mechanisms for understanding atomic-precision doping of Si with B, enabling a number of relevant quantum applications, such as bipolar nanoelectronics, acceptor-based qubits, and superconducting Si.