Perspective and prospects of in situ transmission/scanning transmission electron microscopy.

In situ transmission/scanning transmission electron microscopy (TEM/STEM) measurements have taken a central stage for establishing structure-chemistry-property relationship over the past couple of decades. The challenges for realizing 'a lab-in-gap', i.e. gap between the objective lens pole pieces, or 'a lab-on-chip', to be used to carry out experiments are being met through continuous instrumental developments. Commercially available TEM columns and sample holder, that have been modified for in situ experimentation, have contributed to uncover structural and chemical changes occurring in the sample when subjected to external stimulus such as temperature, pressure, radiation (photon, ions and electrons), environment (gas, liquid and magnetic or electrical field) or a combination thereof. Whereas atomic resolution images and spectroscopy data are being collected routinely using TEM/STEM, temporal resolution is limited to millisecond. On the other hand, better than femtosecond temporal resolution can be achieved using an ultrafast electron microscopy or dynamic TEM, but the spatial resolution is limited to sub-nanometers. In either case, in situ experiments generate large datasets that need to be transferred, stored and analyzed. The advent of artificial intelligence, especially machine learning platforms, is proving crucial to deal with this big data problem. Further developments are still needed in order to fully exploit our capability to understand, measure and control chemical and/or physical processes. We present the current state of instrumental and computational capabilities and discuss future possibilities.

Edge-Confined Excitons in Monolayer Black Phosphorus.

Quantum confinement of two-dimensional excitons in van der Waals materials via electrostatic trapping, lithographic patterning, Moiré potentials, and chemical implantation has enabled significant advances in tailoring light emission from nanostructures. While such approaches rely on complex preparation of materials, natural edges are a ubiquitous feature in layered materials and provide a different approach for investigating quantum-confined excitons. Here, we observe that certain edge sites of monolayer black phosphorus (BP) strongly localize the intrinsic quasi-one-dimensional excitons, yielding sharp spectral lines in photoluminescence, with nearly an order of magnitude line width reduction. Through structural characterization of BP edges using transmission electron microscopy and first-principles GW plus Bethe-Salpeter equation (GW-BSE) calculations of exemplary BP nanoribbons, we find that certain atomic reconstructions can strongly quantum-confine excitons resulting in distinct emission features, mediated by local strain and screening. We observe linearly polarized luminescence emission from edge reconstructions that preserve the mirror symmetry of the parent BP lattice, in agreement with calculations. Furthermore, we demonstrate efficient electrical switching of localized edge excitonic luminescence, whose sites act as excitonic transistors for emission. Localized emission from BP edges motivates exploration of nanoribbons and quantum dots as hosts for tunable narrowband light generation, with future potential to create atomic-like structures for quantum information processing applications as well as exploration of exotic phases that may reside in atomic edge structures.

In Situ Atomic-Scale Probing of the Reduction Dynamics of Two-Dimensional Fe2O3 Nanostructures.

Atomic-scale structural dynamics and phase transformation pathways were probed, in situ, during the hydrogen-induced reduction of Fe2O3 nanostructure bicrystals using an environmental transmission electron microscope. Reduction commenced with the α-Fe2O3 → γ-Fe2O3 phase transformation of one part of the bicrystal, resulting in the formation of a two-phase structure of α-Fe2O3 and γ-Fe2O3. The progression of the phase transformation into the other half of the bicrystalline Fe2O3 across the bicrystalline boundary led to the formation of a single-crystal phase of γ-Fe2O3 with concomitant oxygen-vacancy ordering on every third {422} plane, followed by transformation into Fe3O4. Further reduction resulted in the coexistence of Fe3O4, FeO, and Fe via the transformation pathway Fe3O4 → FeO → Fe. The series of phase transformations was accompanied by the formation of a Swiss-cheese-like structure, induced by the significant volume shrinkage occurring upon reduction. These results elucidated the atomistic mechanism of the reduction of Fe oxides and demonstrated formation of hybrid structures of Fe oxides via tuning the phase transformation pathway.