Recently, we have demonstrated that ultrathin (<30 nm) films of Al2O3 synthesized by (plasma-assisted) atomic layer deposition (ALD) provide an excellent level of surface passivation of c-Si which may find important applications in (high-efficiency) solar cells. In this contribution, the Al2O3 passivation mechanism has been further elucidated by the contactless characterization of the c-Si/Al2O3 interface by optical second-harmonic generation (SHG). SHG has revealed effective field-effect passivation of the c-Si surface caused by a negative fixed charge density of 5??1012 cm-2 in an annealed, 11 nm thick Al2O3 film while it is on the order of 1011 cm??2 in the as-deposited film which shows negligible passivation. A comparison with SHG measurements on a 84 nm thick a-SiNx:H film treated in a conventional firing furnace has revealed the presence of a positive fixed charge density of 2??1012 cm-2 which further corroborates the SHG analysis and results.