Metal‐Assisted Chemical Etching of Silicon in Oxidizing HF Solutions: Origin, Mechanism, Development, and Black Silicon Solar Cell Application

Abstract Metal‐assisted chemical etching (MacEtch) of silicon in oxidizing hydrofluoric acid (HF) solutions has emerged as a prominent top‐down micro/nanofabrication approach for a wide variety of silicon micro/nanostructures. The popularity of the process is due to its simplicity, rapidity, versatility, and scalability. In recent years, there has been a surge of interest in developing MacEtch silicon micro/nanostructures for advanced energy conversion and storage applications, such as photovoltaic devices, thermoelectric devices, lithium‐ion rechargeable batteries, and supercapacitors. Particularly, MacEtch has emerged as a powerful surface micro/nanostructuring method for low‐cost and scalable production of commercial black silicon (b‐Si) with excellent light trapping properties. This review on MacEtch processing of silicon in oxidizing HF solutions provides a critical description of its history and origin including how it evolved into what it is today, the understanding of its mechanism and important technical advances in the field. As regards MacEtch‐fabricated b‐Si, its initial discovery and further improvements to its large‐scale deployment in silicon photovoltaic industry are traced. Some fundamental challenges and perspectives in this exciting field are also discussed.