This manuscript reports an experimental and theoretical study of the transport of potassium ions in thin silicon dioxide films. While alkali contamination was largely researched in the context of MOSFET instability, recent reports indicate that potassium ions can be embedded into oxide films to produce dielectric materials with permanent electric charge, also known as electrets. These electrets are integral to a number of applications, including the passivation of silicon surfaces for optoelectronic devices. In this work, electric field assisted migration of ions is used to rapidly drive K+ into SiO2 and produce effective passivation of silicon surfaces. Charge concentrations of up to ~5 × 1012 e cm−2 have been achieved. This charge was seen to be stable for over 1500 d, with decay time constants as high as 17 000 d, producing an effectively passivated oxide–silicon interface with SRV < 7 cm s−1, in 1 Ω cm n-type material. This level of charge stability and passivation effectiveness has not been previously reported. Overall, this is a new and promising methodology to enhance surface passivation for the industrial manufacture of silicon optoelectronic devices.</p