Voltage‐ and Metal‐assisted Chemical Etching of Micro and Nano Structures in Silicon: A Comprehensive Review

Abstract Sculpting silicon at the micro and nano scales has been game‐changing to mold bulk silicon properties and expand, in turn, applications of silicon beyond electronics, namely, in photonics, sensing, medicine, and mechanics, to cite a few. Voltage‐ and metal‐assisted chemical etching (ECE and MaCE, respectively) of silicon in acidic electrolytes have emerged over other micro and nanostructuring technologies thanks to their unique etching features. ECE and MaCE have enabled the fabrication of novel structures and devices not achievable otherwise, complementing those feasible with the deep reactive ion etching (DRIE) technology, the gold standard in silicon machining. Here, a comprehensive review of ECE and MaCE for silicon micro and nano machining is provided. The chemistry and physics ruling the dissolution of silicon are dissected and similarities and differences between ECE and MaCE are discussed showing that they are the two sides of the same coin. The processes governing the anisotropic etching of designed silicon micro and nanostructures are analyzed, and the modulation of etching profile over depth is discussed. The preparation of micro‐ and nanostructures with tailored optical, mechanical, and thermo(electrical) properties is then addressed, and their applications in photonics, (bio)sensing, (nano)medicine, and micromechanical systems are surveyed. Eventually, ECE and MaCE are benchmarked against DRIE, and future perspectives are highlighted.