Coupling between bulk thermal defects and surface segregation dynamics

Surface segregation is a phenomenon that depends on the delicate interplay between thermodynamic driving forces and kinetic obstacles, for which elevated temperature is often needed to enhance the atom mobility and reach equilibrium. Using the classic system of ${\mathrm{Cu}}₃\mathrm{Au}(100)$ under nonisothermal conditions, herein, we show an adatom process underlying transient surface segregation dynamics through the temperature-change-driven creation and annihilation of thermal vacancies in the bulk and the resulting bulk-surface mass exchanges. This is demonstrated by monitoring the surface composition evolution of ${\mathrm{Cu}}₃\mathrm{Au}(100)$ with temperature changes between 250 and $500{\phantom{\rule{0.16em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$, showing that the increase in temperature decreases monotonically the surface Au concentration as a result of the transfer of more Cu than Au from the bulk to the surface to form Cu-rich clusters of adatoms. Such a bulk thermal defect effect is expected to be universal in inducing the disparity in the bulk-surface mass exchanges of dissimilar atoms in multicomponent materials because of the inherent differences in the vacancy formation energies of the constituent atoms.