Fiber-coupled laser-induced breakdown and Raman spectroscopy for flexible sample characterization with depth profiling capabilities

•LIBS/Raman is effective tool for depth profiling of complex layers.•Calibration-free LIBS is effective analysis tool with flat-beam ablation profile.•LIBS was successful for analysis of Roman bronze artifacts.

A combined laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy system for depth profile analyses is presented. The system incorporates a single 532 nm laser source, which is delivered through an optical fiber to the sample site. The homogenized laser beam results in well-defined cylindrical craters with diameters of 100 μm. LIBS depth profiling analyses of metals was performed applying pulse energies of about 1 mJ. The application of up to 500 pulses allowed to drill through layers of several tens of microns, while observing sharp transitions at the layer interfaces. The capability of the system for Raman spectroscopy was investigated for various polymer samples by reducing the pulse energies below the respective ablation threshold. A combined Raman/LIBS depth profiling was applied to a polymer-coated metal. Additionally, the capability of the system for calibration-free LIBS quantification (CF-LIBS) was evaluated. Quantification of major elements in metallic reference materials showed good agreement with the certified values with relative deviations of less than 30%. Finally, the optimized system was applied for depth profiling and elemental composition analysis of ancient Roman bronze rings. Overall, the presented setup combines the high flexibility of a fiber-coupled system with Raman and micro-LIBS, making the system interesting for depth profiling and elemental quantification in archaeometric as well as industrial applications.