The atomic structure, stability, and dynamics of defects in hexagonal boron nitride (h-BN) are investigated using an aberration-corrected transmission electron microscope operated at 80 kV between room temperature and 1000 °C. At temperatures above 700 °C, parallelogram- and hexagon-shaped defects with zigzag edges become prominent, in contrast to the triangular defects typically observed at lower temperatures. The appearance of 120° corners at defect vertices indicates the coexistence of both N- and B-terminated zigzag edges in the same defect. In situ dynamics studies show that the hexagonal holes grow by electron-induced sputtering of B-N chains, and that at high temperatures these chains can migrate from one defect corner to another. We complement the experiments with first-principles calculation which consider the thermal equilibrium formation energy of different defect configurations. It is shown that, below a critical defect size, hexagonal defects have the lowest formation energy and therefore are the more-stable configuration, and triangular defects are energetically metastable but can be “frozen in” under experimental conditions. We also discuss the possible contributions of several dynamic processes to the temperature-dependent defect formation.

Impact Statement

Study of stability and behavior of various defect in graphene sheets at RT-1000C temperature revealed a feasible and accurate way to control the shapes of h-BN defects, vacancies, edges, and nanopores at the atomic level. This will extend the range of applicatiosn and capabilities of this material.