Chalcogenides by Design: Functionality through Metavalent Bonding and Confinement.

A unified picture of different application areas for incipient metals is presented. This unconventional material class includes several main-group chalcogenides, such as GeTe, PbTe, Sb2 Te3 , Bi2 Se3 , AgSbTe2 and Ge2 Sb2 Te5 . These compounds and related materials show a unique portfolio of physical properties. A novel map is discussed, which helps to explain these properties and separates the different fundamental bonding mechanisms (e.g., ionic, metallic, and covalent). The map also provides evidence for an unconventional, new bonding mechanism, coined metavalent bonding (MVB). Incipient metals, employing this bonding mechanism, also show a special bond breaking mechanism. MVB differs considerably from resonant bonding encountered in benzene or graphite. The concept of MVB is employed to explain the unique properties of materials utilizing it. Then, the link is made from fundamental insights to application-relevant properties, crucial for the use of these materials as thermoelectrics, phase change materials, topological insulators or as active photonic components. The close relationship of the materials' properties and their application potential provides optimization schemes for different applications. Finally, evidence will be presented that for metavalently bonded materials interesting effects arise in reduced dimensions. In particular, the consequences for the crystallization kinetics of thin films and nanoparticles will be discussed in detail.