Precise control of ion energy distribution (IED) is critical to achieve highly selective, low damage etching. A novel approach to control IED using pulsed plasma with synchronously pulsed dc bias on a boundary electrode in Ar gas is first presented. Synchronization of the dc bias applied during the afterglow of a pulsed plasma and the plasma rf power resulted in a double-peaked IED. The mean energies of the two peaks, as well as the peak separation, were controlled by adjusting the applied dc bias and the discharge pressure. Nearly mono-energetic IEDs can be extracted in the afterglow of a pulsed plasma. With precisely controlled IEDs, a new, important phenomenon is reported: photo-assisted etching of p-type Si in chlorine-containing plasma...