Metal-assisted plasma etching (MAPE) of silicon (Si) is an etching technique driven by the catalytic activity of metals such as gold in fluorine-based plasma environments. In this work, we investigated the role of the Si substrate by examining the effects of dopant concentration in both n- and p-type Si and dopant atom type in n-type Si in SF6/O2 mixed gas plasma. At the highest dopant concentrations, both n- and p-type Si initially exhibit inhibition of the MAPE-enhanced etching. As the etch progresses, MAPE initiates, resulting in catalytic etching of the underlying Si at the metal-Si interface. Interestingly, MAPE-enhanced etching increases with decreasing doping concentrations for both n-and type Si substrates, distinct from results for the similar but divergent, metal-assisted chemical etching of silicon in liquid. Our findings show that the metal-Si interface remains essential to MAPE, and surface enrichment of the dopant atoms or other surface chemistries and the size of metal nanoparticles can play roles in modulating catalytic activity.