Laser Ionization Mass Spectrometry at 55: Quo Vadis?

Abstract

Laser ionization mass spectrometry (LIMS) was one of the first practical methods developed for in situ analysis of the surfaces of solid samples. This review will encompass several aspects related to this analytical method. First, we will discuss the process of laser ionization, the influence of the laser type on its performance, and imaging capabilities of this method. In the second chapter, we will follow the historic development of LIMS instrumentation. After a brief overview of the first-generation instruments developed in 1960-1990 years, we will discuss in detail more recent designs, which appeared during the last 2-3 decades. In the last part of our review, we will cover the recent applications of LIMS for surface analysis. These applications include various types of analyses of solid inorganic, organic, and heterogeneous samples, often in combination with depth profiling and imaging capability.

Current Progress in Femtosecond Laser Ablation/Ionisation Time-of-Flight Mass Spectrometry

“…The historic development of LIMS instrumentation is well-documented in a recent review and includes a brief overview of the first-generation instruments and more recent designs developed between 1960 and 1990 [1]. The limited number of femtosecond-LIMS instruments so far is a result of the high price of the fs-laser system and perhaps of the prevailing experience from the nanosecond predecessor of this method about the qualitative rather than quantitative capabilities of LIMS.…”

“…LIMS has a rich history spanning more than 50 years. The initial fast expansion lasted from the middle of the 1970s to the beginning of the 1990s, when it offered the most affordable and fast method of analysing solid samples, including organic and bioorganic compounds [1][2][3]. Several commercial instruments such as LAMMA-500, -1000, -2000 became available in the 1970s [2,[4][5][6][7][8].…”

“…Additionally, we do not consider other important techniques that use laser-based probes, e.g., Fourier Transform Ion Cyclotron Resonance (FT-ICR), Orbitrap or Resonance Ionisation Mass Spectrometry (RIMS). An overview of these studies can be found in the recent review by Azov et al [1]. Our focus on studies with fs-laser ablation source is motivated by its high impact on the quantitative performance and superior chemical imaging capabilities of LIMS.…”

“…The development of LIMS did not stop after a hibernation period in the late 1990s. Current studies show that the critical constraints, such as low accuracy and precision in the elemental and isotope quantification, low mass resolution and considerable interference by abundant polyatomic species have been improved [1,25,26,[29][30][31]. Furthermore, reduced mass spectrometric signal fluctuations, combined with high stability femtosecond laser ablation, pave the way to high-resolution chemical imaging and depth profiling analysis.…”

Imaging isotopic content at the nanoscale using extreme ultraviolet laser ablation and ionization mass spectrometry

“…3,5 Recently, we have shown that an extreme ultraviolet (EUV) laser coupled to a mass spectrometer can also offer unsurpassed three-dimensional (3D) nanoscale spatial resolution for chemical mapping. [12][13][14][15] Our group at Colorado State University (CSU) has built and developed an EUV laser ablation and ionization time-offlight mass spectrometer (EUV TOF) that was the first of its kind to achieve mass spectral imaging with 3D nanoscale spatial resolution. 12,13 The instrument uses a table-top EUV Ar 8+ capillary discharge laser, also developed at CSU, that operates at a wavelength of 46.9 nm (26.4 eV photon energy).…”