Demystifying metal-assisted chemical etching of GaN and related heterojunctions

GaN and related semiconductors have become an increasingly prominent material for a wide range of active and passive devices from optoelectronics to high frequency and power electronics as well as photocatalysis. Regardless of the application, anisotropic etching is required for micro and nano structuring, currently performed by reactive ion etching (RIE). Alternately, metal-assisted chemical etching (MacEtch) is an open-circuit plasma-free anisotropic etching method that has demonstrated high aspect ratio device structures devoid of plasma-induced damage found in RIE. This paper presents an in-depth study of the ensemble electrochemical mechanisms that govern the photo-enhanced MacEtch process of GaN and related heterojunctions. Through in-depth experimental investigations, modeling and simulations, the effects of local cathode and anode design, energy-band alignments, and solution chemistry on MacEtch are correlated with the underlying electronic mechanisms of carrier generation, annihilation, transport, and extraction, establishing a fundamental framework for parametrized prediction of system behavior. These findings carry profound implications for tailored design of photoelectrochemical processes employed not just for uniformly etching wide/ultrawide bandgap materials but more broadly for semiconductor-based photocatalytic reactions in general. One-pot photo-enhanced MacEtching of AlInGaN multi-heterojunction device structures including superlattices and multi-quantum wells are demonstrated.