Surfactant-enabled epitaxy through control of growth mode with chemical boundary conditions

Property coupling at interfaces between active materials is a rich source of functionality, if defect densities are low, interfaces are smooth and the microstructure is featureless. Conventional synthesis techniques generally fail to achieve this when materials have highly dissimilar structure, symmetry and bond type-precisely when the potential for property engineering is most pronounced. Here we present a general synthesis methodology, involving systematic control of the chemical boundary conditions in situ, by which the crystal habit, and thus growth mode, can be actively engineered. In so doing, we establish the capability for layer-by-layer deposition in systems that otherwise default to island formation and grainy morphology. This technique is demonstrated via atomically smooth {111} calcium oxide films on (0001) gallium nitride. The operative surfactant-based mechanism is verified by temperature-dependent predictions from ab initio thermodynamic calculations. Calcium oxide films with smooth morphology exhibit a three order of magnitude enhancement of insulation resistance.