Design and fabrication of superhydrophobic microstructured grooved substrates to suppress the coffee-ring effect and enhance the stability of Sr element detection in liquids using LIBS

Abstract

A new technique has been developed to enhance the stability of laser-induced breakdown spectroscopy (LIBS) in the analysis of dry droplets by mitigating the coffee ring effect (CRE) on substrates with superhydrophobic microstructured grooves. The substrate was prepared from a laser-etched pure copper base, resembling the surface of a lotus leaf, creating a biomimetic superhydrophobic substrate. The superhydrophobic microstructured grooved substrate contained an array of dome-shaped cones with heights of approximately 140 μm and 100 μm, arranged in a periodic pattern of high-low-high. The superhydrophobic properties of the substrate not only evaporation-induced thermal capillary action but also initiated the Marangoni flow, which moves from the periphery to the center of the droplet as it evaporates. This flow mechanism effectively mitigated the CRE by transporting the analyte from the bottom edge of the droplet across its surface to the central peak. To assess how these superhydrophobic microstructured grooved substrates impede the formation of coffee rings, LIBS was deployed to analyze samples from both structured and unstructured grooved substrates. The results indicated that the relative standard deviation (RSD) of the spectral intensity for Sr I at 407.67 nm in substrates with a superhydrophobic microstructured groove edge length of 0.8 mm was 3.6%. In contrast, for the unstructured grooved substrate and a side length of 0.9 mm, the RSD was significantly higher at 25.4%. This research demonstrates that substrates with superhydrophobic microstructured grooves are capable of effectively mitigating the CRE. Additionally, the study examined how the dimensions of these grooves impact the plasma characteristics across two distinct configurations. Based on these observations, calibration curves for Sr were developed using substrates with groove side lengths of 0.6 mm and 0.8 mm. The performance of the superhydrophobic microstructured grooved substrate was satisfactory, exhibiting determination coefficients (R²) of 0.994 and 0.995 for the Sr element. The detection limits (LOD) were notably low at 0.16 μg mL⁻¹ and 0.11 μg mL⁻¹. The average relative standard deviations (ARSD) were 7.2% and 4.9%, respectively. These results demonstrate that the superhydrophobic microstructured grooved substrate effectively mitigates the CRE, thereby enhancing the detection sensitivity and prediction accuracy for heavy metals. This provides a robust reference for selecting platforms using LIBS technology in the pre-treatment process.