Theoretical Investigation on the Microscopic Mechanism of Lattice Thermal Conductivity of ZnXP (X = Si, Ge, and Sn).

Thermal conductivity is an important physical parameter for the application of nonlinear optical single crystal materials. The underlying science of thermal transport behavior is not well established both experimentally and theoretically. In the present work, we have studied the microscopic picture of lattice thermal conductivity of ZnXP (X = Si, Ge, Sn), chalcopyrite ABC type infrared optical crystals, by using a harmonic and anharmonic lattice dynamic method and phonon Boltzmann transport equation based on first-principle calculations. With the mass of atom X increased, the phonon frequencies and phonon group velocities of ZnXP (X = Si, Ge, Sn) are shown not surprisingly to be decreased. Nevertheless, the phonon lifetime of ZnXP is unexpectedly increased, which is the governing mechanism for the increased thermal conductivity as 12.5 W/(m·k), 31.6 W/(m·k), and 35.4 W/(m·k), for ZnSiP, ZnGeP, and ZnSnP, respectively, at 300 K. The contributions of optical phonons (with the frequency below 150 cm) to the total thermal conductivity are remarkable, reaching 18%, 31%, and 34% for three compounds, due to the significantly increased phonon lifetime in the frequency range 50-150 cm. To explore the physical insights of phonon lifetime and phonon anharmonicity, three-phonon scattering phase space and electronic localization function analysis of the X-P bond are provided. The results show that the covalent nature of X-P bonds is enhanced with the increased mass of atom X = Si, Ge, Sn, which induces the reduction of three-phonon scattering phase space in the frequency range 50-150 cm, leading to the enhancement of the phonon lifetime and thermal conductivity of ZnXP.