Chemical Bonding and Crystal Structure Design for Low Thermal Conductivity in Inorganic Solids.

Abstract

Thermal conductivity is one of the fundamental manifestations of how the underlying atomic arrangement in materials facilitates heat flow. The critical role of thermal conductivity in influencing the performance of materials in the energy and quantum technologies arena makes engineering it to match functionality a crucial challenge to address. Here, we focus on intrinsically tuning thermal transport in inorganic crystalline solids through the strategic design of crystal structures. As structure is determined by the underlying chemical bonding, light is also shed on the influence of chemical bonding on thermal transport, including the concept of multicentered bonding and the role of antibonding states. In this review, we distill global research efforts into key design features rooted in chemical bonding and structural principles that enable an intrinsic property-based descriptor-framework for the purposeful manipulation of thermal conductivity in inorganic solids. We survey examples in which lattice thermal conductivity of crystalline solids has been pushed to extremes, specifically toward the diffusion limit or even rendered glassy. The broad and significant applicability of these principles across functional materials such as thermoelectrics, superionic conductors, ferroelectrics and halide perovskites is thus demonstrated. Finally, we explore emerging directions in the field, including topological phonons, thermotronics, and the phonon wave-particle crossover, alongside the impact of artificial intelligence and machine learning on materials discovery.