Structuring of Si into Multiple Scales by Metal‐Assisted Chemical Etching

Abstract Structuring Si, ranging from nanoscale to macroscale feature dimensions, is essential for many applications. Metal‐assisted chemical etching (MaCE) has been developed as a simple, low‐cost, and scalable method to produce structures across widely different dimensions. The process involves various parameters, such as catalyst, substrate doping type and level, crystallography, etchant formulation, and etch additives. Careful optimization of these parameters is the key to the successful fabrication of Si structures. In this review, recent additions to the MaCE process are presented after a brief introduction to the fundamental principles involved in MaCE. In particular, the bulk‐scale structuring of Si by MaCE is summarized and critically discussed with application examples. Various approaches for effective mass transport schemes are introduced and discussed. Further, the fine control of etch directionality and uniformity, and the suppression of unwanted side etching are also discussed. Known application examples of Si macrostructures fabricated by MaCE, though limited thus far, are presented. There are significant opportunities for the application of macroscale Si structures in different fields, such as microfluidics, micro‐total analysis systems, and microelectromechanical systems, etc. Thus more research is necessary on macroscale MaCE of Si and their applications.