Improved limit of detection of a high-resolution fs-LIMS instrument through mass-selective beam blanking

Abstract

Laser Ablation Ionisation Mass Spectrometry (LIMS) is an important quantitative method for chemical analysis of solids. Current limits of detections (LoDs) of LIMS instruments are in the ppm to sub-ppm range (atomic fractions), while other commonly used techniques for solid sample analysis reach LoDs at ppb levels or even below. This study presents the implementation of mass-selective beam blanking in the Laser Mass Spectrometer – Gran Turismo (LMS-GT) to improve the instruments’ detection limit. LMS-GT is a high-performance time-of-flight LIMS instrument coupled to a femtosecond laser ablation ion source reaching micrometre spatial resolutions and mass resolutions ≳ 12′000. A fast high voltage switch was developed in-house to induce potential changes at an Einzel lens at the intermediate time focus of the ion trajectory, leading to short deflections of the ion beam and hindering selected species from reaching the detector. The intensities of single mass lines are reduced with 100% efficiency to below the noise floor when blanked. The detector gain can safely be increased while blanking the most intense mass lines simultaneously, thus improving the detection limit. The LoD of LMS-GT prior to the installation of the mass-selective blanking device was at ppm level (at. frac.) with few sub-ppm detections, the installation pushed it to the lower ppb range, without compromising the initial performance. This emphasises that fs-LIMS can be a powerful quantitative technique for the chemical analysis of solids, with the potential to reach the levels of mass spectrometric analysis achievable with Secondary Ion Mass Spectrometry (SIMS) and Laser Ablation–Inductively Coupled Plasma–Mass Spectrometry (LA-ICP-MS).