Vacancy driven surface disorder catalyzes anisotropic evaporation of ZnO (0001) polar surface

The evaporation and crystal growth rates of ZnO are highly anisotropic and are fastest on the Zn-terminated ZnO (0001) polar surface. Herein, we study this behavior by direct atomic-scale observations and simulations of the dynamic processes of the ZnO (0001) polar surface during evaporation. The evaporation of the (0001) polar surface is accelerated dramatically at around 300 °C with the spontaneous formation of a few nanometer-thick quasi-liquid layer. This structurally disordered and chemically Zn-deficient quasi-liquid is derived from the formation and inward diffusion of Zn vacancies that stabilize the (0001) polar surface. The quasi-liquid controls the dissociative evaporation of ZnO with establishing steady state reactions with Zn and O₂ vapors and the underlying ZnO crystal; while the quasi-liquid catalyzes the disordering of ZnO lattice by injecting Zn vacancies, it facilitates the desorption of O₂ molecules. This study reveals that the polarity-driven surface disorder is the key structural feature driving the fast anisotropic evaporation and crystal growth of ZnO nanostructures along the [0001] direction.