Recovery of Quantitative Secondary Ion Mass Spectrometry under External Perturbations Relevant to In Situ and Operando Measurements

Abstract In situ and operando characterization techniques are becoming increasingly important for investigating electronic materials and devices. Although secondary ion mass spectrometry (SIMS) offers unmatched sensitivity, quantitative in situ and operando SIMS remains largely unexplored because external perturbations disturb ion optical conditions and quantitative calibration. Here, representative magnetic, electrical, and optical perturbations were investigated, and a practical strategy for recovering quantitative SIMS was demonstrated. Conventional restoration of the primary and secondary ion optics failed to provide reproducible dopant-to-matrix intensity ratios, yielding coefficients of variation between 26.2% and 54.6%. Introducing individually optimized extraction parameters reduced this variability to 0.3−1.1%. Long-term reproducibility was evaluated using 866 measurements of boron- and phosphorus-implanted reference materials acquired over approximately 6.5 years. Despite repeated source replacements and maintenance procedures, the calibrated dose and projected range remained reproducible with coefficients of variation below 1%. Finally, quantitative validation was performed using implanted reference materials measured under all investigated perturbations. Although the raw SIMS profiles differed substantially in both signal intensity and apparent depth scale, perturbation-specific calibration resulted in closely overlapping dopant distributions. These results demonstrate that perturbation-specific calibration and extraction optimization can restore reproducible quantitative SIMS response under selected externally imposed perturbations, providing a metrological basis for the further development of quantitative in situ and operando SIMS.