Applications of Transmission Electron Microscopy in Phase Engineering of Nanomaterials.

Phase engineering of nanomaterials (PEN) is an emerging field that aims to tailor the physicochemical properties of nanomaterials by precisely manipulating their crystal phases. To advance PEN effectively, it is vital to possess the capability of characterizing the structures and compositions of nanomaterials with precision. Transmission electron microscopy (TEM) is a versatile tool that combines reciprocal-space diffraction, real-space imaging, and spectroscopic techniques, allowing for comprehensive characterization with exceptional resolution in the domains of time, space, momentum, and, increasingly, even energy. In this Review, we first introduce the fundamental mechanisms behind various TEM-related techniques, along with their respective application scopes and limitations. Subsequently, we review notable applications of TEM in PEN research, including applications in fields such as metallic nanostructures, carbon allotropes, low-dimensional materials, and nanoporous materials. Specifically, we underscore its efficacy in phase identification, composition and chemical state analysis, observations of phase evolution, as well as the challenges encountered when dealing with beam-sensitive materials. Furthermore, we discuss the potential generation of artifacts during TEM imaging, particularly in scanning modes, and propose methods to minimize their occurrence. Finally, we offer our insights into the present state and future trends of this field, discussing emerging technologies including four-dimensional scanning TEM, three-dimensional atomic-resolution imaging, and electron microscopy automation while highlighting the significance and feasibility of these advancements.