Chemical Tomography

Laser-assisted microanalysis offers the advantage of determining the spatially resolved compositions in 3D.  However, the requirement to analyse smaller and smaller length-scales is challenged by focal diffraction as well as reduction of sensitivity at the nano-scale.

Fundamental Mechanisms

 Using XUV pulses, a significant enhancement of the resolution is accomplished thanks to a much shorter wavelength, with respect to state-of-the-art commercial lasers. Furthermore, as the most innovative aspect, the sampling efficiency is enhanced using “ionizing radiation”, i.e. directly activating the target material. The high photon-energy (20–100 eV) makes the sampling process essentially single-photon, whatever bond or ionization energy. Furthermore, the analytical setup is simplified to a sampling source and detector, i.e. without the need for a secondary ionization or excitation source as in some state-of-the-art analytical systems. In this review, fundamental aspects of X-ray laser desorption and ablation are discussed, and a survey of the available literature is presented. The main objective is to convince the reader that desorption or ablation in this spectral domain is a significantly cleaner sampling process, with large potential, still requiring investigation for a complete fundamental understanding. Applications of laser microanalysis are thus entering the nano-scale era, which shrinks the gap with electron-based microprobes.

Photovoltaic Thin-Films
Direct nano-scale microanalysis is important for photovoltaic functional thin films to characterize their homogeneity and purity. This demands combining spatial resolution in the micro/nano-scale and sensitivity in the trace-level range, which is at the moment beyond state-of-the-art. As dictated by counting statistics, the reduction of the spot size degrades the detection limit. The utilization of a tabletop XUV laser at λ = 46.9 nm has shown to dramatically improve the ablation efficiency with respect to that of visible lasers, such that ablation spot of 1 μm limits. Li-doped Cu2ZnSn(S,Se)4 (so-called kesterite) thin films were irradiated across 3D ablation arrays for hyperspectral mapping by means of time-of-flight mass spectrometry. The nominal 3D data node lattices were the initialisation perceptron, filled with measured values, and for a detailed supervised learning postprocessing, the node-to-node links were analysed by means of a 2D-kernel covariance algorithm. The latter permitted to obtain robust 3D elemental distribution functions well below the measurement spacing, giving insights into the inhomogeneity and impurities.


Water-Oxidation Catalysts

Nanoscale depth profiling analysis of a CoNCN-coated electrode for water oxidation catalysis was carried out using table-top extreme ultraviolet (XUV) laser ablation time-of-flight mass spectrometry. The self-developed laser operates at λ = 46.9 nm and represents factor of 4 reduction in wavelength with respect to the 193 nm excimer laser. The reduction of the wavelength is an alternative approach to the reduction of the pulse duration, to enhance the ablation characteristics and obtain smaller quasi-nondestructive ablation pits. Such a XUV-laser ablation method allowed distinguishing different composite components of the catalyst-Nafion blend, used to modify a screen-printed carbon electrode surface. Chemical information was extracted by fragment assignment and relative amplitude analysis of the mass spectrometry peaks. Pure Nafion and the exposed carbon substrate were compared as references. Material specific fragments were clearly identified by the detected nonoverlapping mass-to-charge peaks of Nafion and CoNCN. Three dimensional mapping of relevant mass peak amplitudes was used to determine the lateral distribution and to generate depth profiles from consecutive laser pulses. Evaluating the profiles of pristine electrodes gave insight into fragmentation behavior of the catalyst in a functional ionomer matrix and comparison of post-catalytic electrodes revealed spots of thin localized Co residues.



Qu, D.; Ohannessian, N.; Wyder, C.; Trottmann, M.; Wichser, A.; Lippert, T.; Bleiner, D. High-precision mapping of fluorine and lithium in energy materials by means of laser-induced XUV spectroscopy (LIXS). Spectrochim. Acta B 2021, 181, 106214 (7 pp.).
Detailed Record
Bleiner, D.; Trottmann, M.; Müller, R.; Rush, L.; Kuznezov, I.; Cabas-Vidani, A.; Romanyuk, Y.; Tiwari, A.; Patzke, G. R.; Menoni, C. S.; et al. 3D chemical mapping of thin films by means of X-ray laser microanalysis. In X-ray lasers 2018. Proceedings of the 16th international conference on X-ray lasers, presented at the 16th international conference on X-ray lasers (ICXRL 2018), Prague, Czech Republic, October 7-12, 2018; Kozlová, M., Nejdl, J., Eds.; Springer proceedings in physics; Springer: Cham, 2020; Vol. 241, pp 3-10.
Detailed Record
Bleiner, D.; Juha, L.; Qu, D. Soft X-ray laser ablation for nano-scale chemical mapping microanalysis. J. Anal. At. Spectrom. 2020, 35 (6), 1051-1070.
Detailed Record
Bleiner, D.; Trottmann, M.; Cabas-Vidani, A.; Wichser, A.; Romanyuk, Y. E.; Tiwari, A. N. XUV laser mass spectrometry for nano-scale 3D elemental profiling of functional thin films. Appl. Phys. A 2020, 126, 230 (10 pp.).
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Barbato, F.; Atzeni, S.; Batani, D.; Bleiner, D.; Boutoux, G.; Brabetz, C.; Bradford, P.; Mancelli, D.; Neumayer, P.; Schiavi, A.; et al. Quantitative phase contrast imaging of a shock-wave with a laser-plasma based X-ray source. Sci. Rep. 2019, 9 (1), 18805 (11 pp.).
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