First-principles study of negative thermal expansion in zinc oxide

We present the first-principles calculations of vibrational and thermal properties for wurtzite and zinc-blende zinc oxide (ZnO) within DFT and quasi-harmonic approximation, especially for their negative thermal expansion (NTE) behavior. For the wurtzite and zinc-blende phases, negative thermal expansions are obtained at T < 95 K and T < 84 K, respectively. For the wurtzite structure, calculated phonon frequencies and mode Grüneisen parameters of low-energy modes are in good agreement with that determined experimentally. And the thermal expansion coefficient is found to be in good agreement with the experimental results. Like many other NTE semiconductors, detailed study of both phases shows that maximum contribution to NTE comes from low-frequency transverse acoustic modes, while for the wurtzite structure the contribution of longitudinal acoustic and lowest-energy optical modes is not ignorable. From the specific analysis of the vibration modes, we found that the negative thermal expansion in ZnO is dominated by the tension effect.