Back to the Basics: Probing the Role of Surfaces in the Experimentally Observed Morphological Evolution of ZnO

Although the physics and chemistry of materials are driven by exposed surfaces in the morphology, they are fleeting, making them inherently challenging to study experimentally. The rational design of their morphology and delivery in a synthesis process remains complex because of the numerous kinetic parameters that involve the effective shocks of atoms or clusters, which end up leading to the formation of different morphologies. Herein, we combined functional density theory calculations of the surface energies of ZnO and the Wulff construction to develop a simple computational model capable of predicting its available morphologies in an attempt to guide the search for images obtained by field-emission scanning electron microscopy (FE-SEM). The figures in this morphology map agree with the experimental FE-SEM images. The mechanism of this computational model is as follows: when the model is used, a reaction pathway is designed to find a given morphology and the ideal step height in the whole morphology map in the practical experiment. This concept article provides a practical tool to understand, at the atomic level, the routes for the morphological evolution observed in experiments as well as their correlation with changes in the properties of materials based solely on theoretical calculations. The findings presented herein not only explain the occurrence of changes during the synthesis (with targeted reaction characteristics that underpin an essential structure-function relationship) but also offer deep insights into how to enhance the efficiency of other metal-oxide-based materials via matching.