Anomalous Lattice Thermal Conductivity in Rocksalt IIA-VIA Compounds

TL;DR

This study investigates the microscopic mechanisms behind anomalously low lattice thermal conductivity in certain rocksalt-structured compounds, revealing key phonon interactions and effects of strain that can guide the design of thermally insulating materials.

Contribution

It identifies specific phonon-related factors responsible for low thermal conductivity in rocksalt compounds and demonstrates how strain can further reduce k$_L$, offering new insights for material design.

Findings

Low k$_L$ in BaO, BaS, MgTe despite low atomic mass.

Phonon softening and mode overlap increase scattering.

Strain enhances phonon softening and reduces thermal conductivity.

Abstract

Materials with an intrinsic (ultra)low lattice thermal conductivity (k$_L$) are critically important for the development of efficient energy conversion devices. In the present work, we have investigated microscopic origins of low k$_L$ behavior in BaO, BaS and MgTe by exploring lattice dynamics and phonon transport of 16 iso-structural MX (Mg, Ca, Sr, Ba and X = O, S, Se and Te) compounds in the rocksalt (NaCl)-type structure by comparing their lattice transport properties with the champion thermoeletric iso-structural material, PbTe. Anomalous trends are observed for k$_L$ in MX compounds except the MgX series in contrast to the expected trend from their atomic mass. The underlying mechanisms for such low k$_L$ behavior in relatively low atomic mass systems namely BaO, BaS and MgTe compounds are thoroughly analyzed. We propose the following dominant factors that might be responsible for low k$_L$ behavior in these materials: 1) softening of transverse acoustic (TA) phonon modes despite low atomic mass, 2) low lying optic (LLO) phonon modes fall deep into acoustic mode region which enhances overlap between longitudinal acoustic (LA) and LLO phonon modes which increases scattering phase space, 3) short phonon lifetimes and high scattering rates, 4) relatively high density (\r{ho}) and large Gr\"uneisen parameter. Moreover, tensile strain also causes a further reduction in k$_L$ for BaO, BaS and MgTe through phonon softening and near ferroelectric instability. Our comprehensive study on 16 binary MX compounds might provide a pathway for designing (ultra)low k$_L$ materials even with simple crystal systems through phonon engineering.