Improving the accuracy of high-repetition-rate LIBS based on laser ablation and scanning parameters optimization.

Laser-induced breakdown spectroscopy system based on high-repetition-rate microchip laser (HR-LIBS) has been widely used in elemental analysis due to its high energy stability, good portability and fast spectral acquisition speed. However, repeated ablation on powder pellets like soil and coal using HR-LIBS system encounters the problem of serious decline in measurement accuracy. In this work, the relationship between laser ablation and scanning parameters, their correlation with spectral intensity, as well as the optimization approach were fundamentally studied. The correlations among the crater overlapping rate, crater depth and spectral intensity were obtained. An HR-LIBS system with microchip laser (4 kHz repetition rate, 100 µJ laser pulse energy) to perform repeated scanning ablation was established. A theoretical model of the ablation crater morphology for repeated scanning ablation was developed. By taking soil pellets as the experimental samples, the linear fitting curves of crater depth and the spectral intensity ratio were established with the R2 of 0.90∼0.99. The experimental results showed that as the crater depth developed during repeated ablation, the Si-normalized spectral intensity decreased, and thus the spectral repeatability decreased. It was found that by optimizing the overlapping rate to form a flat crater bottom, the confinement effect of the crater on the plasma could be avoided. As a result, the spectral repeatability was significantly improved. The relative standard deviation (RSD) of Si-normalized spectral intensity was improved from 5% to 0.6%. Finally, repeated ablation was performed with the optimized overlapping rate on soil pellets. The R2 of calibration curves of Fe, Mg, Ca, and Al were all above 0.993, and the average RSDs were between 0.5% and 1%. This study provides a fast, accurate, and stable method for the analysis of the samples consisting of various materials with high heterogeneity.