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

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-08, Vol.20 (35), p.e2400499-n/a
• Main Authors: Surdo, Salvatore, Barillaro, Giuseppe
• Format: Article
• Language: English
• Subjects: biosensing; Chemical etching; Electric potential; electrochemical etching; Electrolytes; Etching; Machining; medicine; metal‐assisted etching; microstructure; microsystems; Nanostructure; Optical properties; Photonics; Reactive ion etching; Silicon; Voltage
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202400499

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. Here, the key mechanisms and diverse applications of controlled voltage‐assisted chemical etching (ECE) and metal‐assisted chemical etching (MaCE) of silicon, spanning both micro and nanoscale dimensions, are reviewed. This review offers a distinctive understanding of ECE and MaCE technologies, highlighting the most recent achievements, and discussing their future perspectives in silicon micro and nano machining.