Why thermal conductivity of CaO is lower than that of CaS: a study from the perspective of phonon splitting of optical mode.

Generally speaking, for materials with the same structure, the thermal conductivity is higher for lighter atomic masses. However, we found that the thermal conductivity of CaO is lower than that of CaS, despite the lighter atomic mass of O than S. To uncover the underlying physical mechanisms, the thermal conductivity of CaM (M = O, S, Se, Te) and the corresponding response to strain is investigated by performing first-principles calculations along with the phonon Boltzmann transport equation. For unstrained system, the order of thermal conductivity is CaS > CaO > CaSe > CaTe. This order remains unchanged in the strain range of -2% to 5%. When the compressive strain is larger than 2%, the thermal conductivity of CaO surpasses that of CaS and becomes the highest thermal conductivity material among the four compounds. By analyzing the mode-dependent phonon properties, the phonon lifetime is found to be dominant over other influential factors and leads to the disparate response of thermal conductivity under strain. Moreover, the changing trend of three-phonon scattering phase space is consistent with that of phonon lifetime, which is directly correlated to the phonon frequency gap induced by the LO-TO splitting. The variation of Born effective charge is found to be opposite for CaM. The Born effective charge of CaO decreases with tensile strain increasing, demonstrating stronger charge delocalization and lower ionicity, while the Born effective charges of CaS, CaSe, and CaTe show a dramatic increase. Such variation indicates that the bonding nature can be effectively tuned by external strain, thus affecting the phonon anharmonic properties and thermal conductivity. The difference of bonding nature is further confirmed by the band structure. Our results show that the bonding nature of CaM can be modulated by external strain and leads to disparate strain dependent thermal conductivity.