Quantitative Interleaved-Pulse Acquisition Extends the Range of Isotope-Ratio Measurements in ToF-SIMS

Abstract: Isotope ratios underpin tracer studies of transport in oxides, battery materials, and biological systems, yet time-of-flight secondary ion mass spectrometry (ToF-SIMS) struggles to quantify ratios whose members differ in intensity by orders of magnitude: a primary-ion pulse long enough to count the minor isotope precisely can saturate the major isotope, whereas a pulse short enough to keep the major isotope linear yields too few minor-isotope counts. We show that multi-pulse-width acquisition yields quantitative isotope ratios when a dose factor measured within each crater links the phases and each isotope is taken only from phases in which it remains linear; we call this quantitative reconstruction interleaved-pulse acquisition. Pulse widths are selected from measured transfer curves and peak shapes. On thermal SiO2, a tuned (6, 35) ns pair achieves the same per-layer precision as short-pulse acquisition with a 13-fold reduction in the number of analysis frames. On 18O-enriched WOx films, interleaving extends the quantifiable range at the low-fraction end by about 14-fold. Across isotope ratios spanning approximately 1:500 to 1:1, the interleaved reconstruction agrees with the corresponding linear reference measurements, showing no measurable bias introduced by interleaving, and natural-abundance ratios of oxygen, strontium and titanium are reproduced within several percent. The method requires no hardware additions and enables depth-resolved isotope-ratio measurements over a wide range within a single crater.