π‐Phase Tin and Germanium Monochalcogenide Semiconductors: An Emerging Materials System

Abstract Cubic π‐phase monochalcogenides (MX, M = Sn, Ge; X = S, Se) are an emerging new class of materials that has recently been discovered. Here, their thermodynamic stability, progress in synthetic routes, properties, and prospective applications are reviewed. The thermodynamic stability is demonstrated through density functional theory total energy and phonon spectra calculations, which show that the π‐phase polytype is stable across the monochalcogenide family. To date, only π‐phase tin monochalcogenides have been observed experimentally while π‐phase Ge‐monochalcogenides are predicted to be stable but are yet to be experimentally realized. Various synthetic preparation protocols of π‐SnS and π‐SnSe are described, focusing on surfactant‐assisted nanoparticle synthesis and chemical deposition of thin films from aqueous‐bath compositions. These techniques provide materials with different surface energies, which are likely to play a major role in stabilizing the π‐phase in nanoscale materials. The properties of this newly discovered family of semiconducting materials are discussed in comparison with their conventional orthorhombic polymorphs. These could benefit a number of photovoltaic and optoelectronic applications since, apart from being cubic, they also possess characteristic advantages, such as moderately low toxicity and natural abundance.