Evaluation of microscale crystallinity modification induced by laser writing on Mn₃O₄ thin films

Defining microstructures and managing local crystallinity allow the implementation of several functionalities in thin film technology. The use of ultrashort Bessel beams for bulk crystallinity modification has garnered considerable attention as a versatile technique for semiconductor materials, dielectrics, or metal oxide substrates. The aim of this work is the quantitative evaluation of the crystalline changes induced by ultrafast laser micromachining on manganese oxide thin films using micro-Raman spectroscopy. Pulsed Bessel beams featured by a 1 mu m-sized central core are used to define structures with high spatial precision. The dispersion relation of Mn3O4 optical phonons is determined by considering the conjunction between X-ray diffraction characterization and the phonon localization model. The asymmetries in Raman spectra indicate phonon localization and enable a quantitative tool to determine the crystallite size at micrometer resolution. The results indicate that laser-writing is effective in modifying the low-crystallinity films locally, increasing crystallite sizes from similar to 8 nm up to 12 nm, and thus highlighting an interesting approach to evaluate laser-induced structural modifications on metal oxide thin films.