Fabrication of Gold-Silicon Nanostructured Surfaces with Reactive Laser Ablation in Liquid

Laser processing is an emerging technique capable of synthesizing metal-silicon composite surfaces for various applications. However, little is known about the chemical composition of these laser-processed surfaces, and the reaction mechanisms leading to their formation are poorly understood. In this work, we report the formation of gold-silicon nanostructured surfaces through reactive laser ablation in liquid. Silicon wafers were immersed in pH-controlled solutions of KAuCl₄ and processed with ultrashort laser pulses. Gold deposition on the silicon wafers was found to depend on the pH of the precursor solution: neutral solutions (pH ∼6.3) resulted in much higher gold deposition than acidic or basic solutions. Laser processing of silicon wafers in water followed by immersion in the KAuCl₄ solution resulted in lower gold deposition. X-ray photoelectron spectroscopy and depth profiling showed the existence of both gold (Au⁰) and gold-silicide (AuSi) phases on the surfaces. Under both types of processing conditions, the gold atomic fraction and gold-silicide content increased with depth to at least 150 nm into the surface of the silicon wafer, although significantly more gold and gold-silicide were formed when the silicon was ablated in KAuCl₄ solution as compared to immersion in KAuCl₄ after ablation in water. Based on these data and existing literature on laser processing of silicon, we propose mechanisms that explain the observed gold penetration depth and its deposition dependence on solution pH. The mechanistic understanding gained in this work may be useful for synthesizing a variety of metal-silicon composite surfaces through laser processing to prepare functional materials such as catalysts and surface-enhanced Raman spectroscopy substrates.