Accuracy of a reference-free Monte Carlo approach for SEM-EDS thickness assessment of TiN coatings onto diverse substrates

•EDS experiments and Monte Carlo modeling allowed to assess the coating thickness.•Thicknesses were assessed from a single EDS spectrum using no reference materials.•Accuracy of thicknesses assessed is sensitive to the microscope operational conditions.•For V0 higher than 20 kV, 90 % of predicted thicknesses showed accuracy better than 85 %.