In SIMS analysis of III-V compound semi-conductors with different matrix composition multi-layer, quantification of impurity or dopant is complex due to matrix effect. When we investigated relative sensitivity factor (RSF) of Si (n-type dopant) in each matrix and calculated RSF ratio, it seems to vary depending on offset voltage to sample. In this paper, we have investigated RSF of Si in various III-V compound semi-conductor. In acquiring RSF of Si, offset voltage on sample during the measurement and reference intensity (IR) in RSF calculation were adopted as parameter. In the case of some matrix sample, energy distribution was examined, and it proved that the energy distribution of Si and V group element (P and As) is concerned in RSF ratio. RSF ratio does not depend on offset voltage if IR in RSF calculation is employed in the same matrix as that of Si. As in the case with previous study, the matrix effect of Si in InP and InGaAs reveals at the peak of energy distribution. Copyright © 2012 John Wiley & Sons, Ltd.