Understanding Defects in Amorphous Silicon with Million‐Atom Simulations and Machine Learning

The structure of amorphous silicon (a‐Si) is widely thought of as a fourfold‐connected random network, and yet it is defective atoms, with fewer or more than four bonds, that make it particularly interesting. Despite many attempts to explain such “dangling‐bond” and “floating‐bond” defects, respectively, a unified understanding is still missing. Here, we use advanced computational chemistry methods to reveal the complex structural and energetic landscape of defects in a‐Si. We study an ultra‐large‐scale, quantum‐accurate structural model containing a million atoms, and thousands of individual defects, allowing reliable defect‐related statistics to be obtained. We combine structural descriptors and machine‐learned atomic energies to develop a classification of the different types of defects in a‐Si. The results suggest a revision of the established floating‐bond model by showing that fivefold‐bonded atoms in a‐Si exhibit a wide range of local environments–analogous to fivefold centers in coordination chemistry. Furthermore, it is shown that fivefold (but not threefold) coordination defects tend to cluster together. Our study provides new insights into one of the most widely studied amorphous solids, and has general implications for understanding defects in disordered materials beyond silicon alone. Machine‐learning methods and computational chemistry are combined to develop a comprehensive understanding of coordination defects in amorphous silicon. Fivefold‐connected atoms fall into three categories based on their chemical structure, and are found to cluster together, which can be explained based on energetic arguments.