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.

Abstract Highly efficient organic–inorganic hybrid solar cells of Si‐poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) have been demonstrated by simultaneous structural, electrical, and interfacial engineering with low processing temperature. Si substrate has been sculpted into hierarchical structure to reduce light reflection loss and increase interfacial junction area at the same time. Regarding the electrical optimization, highly conductive organic PEDOT:PSS layer has been formulated with low sheet resistance. It is argued that the sheet resistance, rather than conductivity, is the primary parameter for the high efficiency hybrid cells, which leads to the optimization of thickness, i.e., thick enough to have low sheet resistance but transparent enough to pass the incident sunlight. Finally, siloxane oligomers have been inserted into top/bottom interfaces by contact‐printing at room ambient, which suppresses carrier recombination at interfaces and reduces contact resistance at bottom electrode. Contrary to high‐temperature doping (for the formation of front surface or back surface fields), wet solution processes or vacuum‐based deposition, the contact‐printing can be done at room ambient to reduce carrier recombination at the interfaces. The high efficiency obtained with low processing temperature can make this type of cells be a possible candidate for post‐Si photovoltaics.