Assessing dead time effects when attempting isotope ratio quantification by time-of-flight secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a quasi-non-destructive technique capable of analyzing the outer monolayers of a solid sample and detecting all elements of the periodic table and their isotopes. Its ability to analyze the outer monolayers resides in sputtering the sample surface with a low-dose primary ion gun, which, in turn, imposes the use of a detector capable of counting a single ion at a time. Consequently, the detector saturates when more than one ion arrives at the same time hindering the use of TOF-SIMS for quantification purposes such as isotope ratio estimation. Even though a simple Poisson-based correction is usually implemented in TOF-SIMS acquisition software to compensate the detector saturation effects, this correction is only valid up to a certain extent and can be unnoticed by the inexperienced user. This tutorial describes a methodology based on different practices reported in the literature for dealing with the detector saturation effects and assessing the validity limits of Poisson-based correction when attempting to use TOF-SIMS data for quantification purposes. As a practical example, a dried lithium hydroxide solution was analyzed by TOF-SIMS with the aim of estimating the ⁶Li/⁷Li isotope ratio. The approach presented here can be used by new TOF-SIMS users on their own data for understanding the effects of detector saturation, determine the validity limits of Poisson-based correction, and take into account important considerations when treating the data for quantification purposes.