Defect engineering in semiconductor-based SERS

Semiconductor-based surface enhanced Raman spectroscopy (SERS) platforms take advantage of the multifaceted tunability of semiconductor materials to realize specialized sensing demands in a wide range of applications. However, until quite recently, semiconductor-based SERS materials have generally exhibited low activity compared to conventional noble metal substrates, with enhancement factors (EF) typically reaching 10³, confining the study of semiconductor-based SERS to purely academic settings. In recent years, defect engineering has been proposed to effectively improve the SERS activity of semiconductor materials. Defective semiconductors can now achieve noble-metal-comparable SERS enhancement and exceedingly low, nano-molar detection concentrations towards certain molecules. The reason for such success is that defect engineering effectively harnesses the complex enhancement mechanisms behind the SERS phenomenon by purposefully tailoring many physicochemical parameters of semiconductors. In this perspective, we introduce the main defect engineering approaches used in SERS-activation, and discuss in depth the electromagnetic and chemical enhancement mechanisms (EM and CM, respectively) that are influenced by these defect engineering methods. We also introduce the applications that have been reported for defective semiconductor-based SERS platforms. With this perspective we aim to meet the imperative demand for a summary on the recent developments of SERS material design based on defect engineering of semiconductors, and highlight the attractive research and application prospects for semiconductor-based SERS.