The plasma catalyzed deposition of compound dielectrics is very common for surface passivation of Si-based solar cells in recent decades. This paper reviews the underlying physics and chemistry of chemically active plasmas for the deposition of dielectric films including hydrogenated amorphous silicon nitride (a-SiNx:H), aluminum oxide (Al2O3) and hydrogenated amorphous silicon oxide (a-SiOx:H). The relevant growth and passivation mechanisms are identified and several examples are selected to represent the superiority of plasma processes in the application of Si photovoltaics. (C) 2015 Elsevier B.V. All rights reserved.