Three-Fold Coordination of Copper in Sulfides: A Blockade for Hole Carrier Delocalization but a Driving Force for Ultralow Thermal Conductivity

Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu 3 BiS 3 with those of tetrahedrite (Cu 12 Sb 4 S 13 ) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å 2 . Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu 3 BiS 3 and in other copper-rich sulfides constituted of interconnected CuS 3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu + /Cu 2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu–S network is built of CuS 4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.