First-principles investigation of negative thermal expansion in II-VI semiconductors

Within the framework of first-principles, all II-VI semiconductors with cubic zinc blende structure have negative thermal expansion (NTE) behavior at low temperatures. Negative mode Grüneisen parameters are found for two transverse acoustic (TA) branches near the Brillouin-zone boundaries. Through the analysis of vibrational modes, it shows that the librational mode which brings about the bond tension effect by atomic motions perpendicular to the bonds can contribute to the NTE. Related thermodynamic properties of II-VI semiconductors have also been studied. It is demonstrated that with increased ionic radius and atomic mass, the variety of electronegativity can cause more covalent character in bonding nature, weaker interatomic force constants and lower frequencies in lattice vibrations. Thus, despite the same vibrational modes, II-VI semiconductors can present different NTE behavior and thermodynamic properties. - Highlights: • The NTE properties of II-VI semiconductors are investigated by first-principles calculation. • Negative mode Grüneisen parameters are found for two TA branches. • The librational mode can contribute to the NTE behavior. • Various ionic radius and electronegativity can cause different NTE behavior and thermodynamic properties