Hidden Local Symmetry Breaking in Silver Diamondoid Compounds is Root Cause of Ultralow Thermal Conductivity

Abstract Typically, conventional structure transitions occur from a low symmetry state to a higher symmetry state upon warming. In this work, an unexpected local symmetry breaking in the tetragonal diamondoid compound AgGaTe₂ is reported, which, upon warming, evolves continuously from an undistorted ground state to a locally distorted state while retaining average crystallographic symmetry. This is a rare phenomenon previously referred to as emphanisis. This distorted state, caused by the weak sd³ orbital hybridization of tetrahedral Ag atoms, causes their displacement off the tetrahedron center and promotes a global distortion of the crystal structure resulting in strong acoustic–optical phonon scattering and an ultralow lattice thermal conductivity of 0.26 W m⁻¹ K⁻¹ at 850 K in AgGaTe₂. The findings explain the underlying reason for the unexpectedly low thermal conductivities of silver‐based compounds compared to copper‐based analogs and provide a guideline to suppressing heat transport in diamondoid and other materials.