In this work, we demonstrate a noninvasive and contactless optical metrology technique to assess the quantitative electron trapping-detrapping in a semiconductor/dielectric structure and examine its correlation with oxide thickness. The experimental measurements are conducted with a home-built instrument that captures the time-dependent optical second-harmonic signal from the Si/SiO 2 interface. A numerical model is implemented to analyze the quantitative charge trapping-detrapping over time and determine charge retention time in the Si/SiO 2 structure while correlating it with experimental results.