Ferroelectric freestanding hafnia membranes with metastable rhombohedral structure down to 1-nm-thick.

Two-dimensional freestanding membranes of materials, which can be transferred onto and make interfaces with any material, have attracted attention in the search for functional properties that can be utilized for next-generation nanoscale devices. We fabricated stable 1-nm-thick hafnia membranes exhibiting the metastable rhombohedral structure and out-of-plane ferroelectric polarizations as large as 13 µC/cm2. We also found that the rhombohedral phase transforms into another metastable orthorhombic phase without the ferroelectricity deteriorating as the thickness increases. Our results reveal the key role of the rhombohedral phase in the scale-free ferroelectricity in hafnia and also provide critical insights into the formation mechanism and phase stability of the metastable hafnia. Moreover, ultrathin hafnia membranes enable heterointerfaces and devices to be fabricated from structurally dissimilar materials beyond structural constrictions in conventional film-growth techniques.

Artifactual atomic displacements on surfaces using annular dark-field images with image simulation.

We investigated artifactual atomic displacements on a Pt (111) surface using annular dark-field (ADF) scanning transmission electron microscopy (STEM) images under ideal conditions with multi-slice image simulation. Pt atomic columns on the surface exhibited artifact displacement. The bright spots shifted slightly toward the interior of the crystal, indicating that ADF imaging underestimates atomic distance measurements on the crystal surface. Multiple peak fitting is an effective method for determining the positions of bright spots and obtaining more accurate atomic positions while reducing the impact of surface-related artifacts. This is important for the measurement of interatomic distances on crystal surfaces, particularly for catalyst particles.

Direct imaging of local atomic structures in zeolite using optimum bright-field scanning transmission electron microscopy.

Zeolites are used in industries as catalysts, ion exchangers, and molecular sieves because of their unique porous atomic structures. However, direct observation of zeolitic local atomic structures via electron microscopy is difficult owing to low electron irradiation resistance. Subsequently, their fundamental structure-property relationships remain unclear. A low-electron-dose imaging technique, optimum bright-field scanning transmission electron microscopy (OBF STEM), has recently been developed. It reconstructs images with a high signal-to-noise ratio and a dose efficiency approximately two orders of magnitude higher than that of conventional methods. Here, we performed low-dose atomic-resolution OBF STEM observations of two types of zeolite, effectively visualizing all atomic sites in their frameworks. In addition, we visualized the complex local atomic structure of the twin boundaries in a faujasite (FAU)-type zeolite and Na+ ions with low occupancy in eight-membered rings in a Na-Linde Type A (LTA) zeolite. The results of this study facilitate the characterization of local atomic structures in many electron beam-sensitive materials.

Ultra-high contrast STEM imaging for segmented/pixelated detectors by maximizing the signal-to-noise ratio.

Atomic-resolution low-dose imaging for beam-sensitive materials is one of the most challenging topics in electron microscopy research. In this study, we theoretically developed a new scanning transmission electron microscopy (STEM) imaging technique by maximizing the signal-to-noise ratio of an obtainable image under the weak phase object approximation (WPOA), which we will call optimum bright-field (OBF) imaging. OBF images are obtained by processing multiple images acquired by segmented/pixelated detectors through complex frequency filtering. This method has been confirmed through a systematic image simulation to be highly dose-efficient. Furthermore, we experimentally demonstrate the high dose efficiency of the OBF technique by visualizing the atomic structure in a lithium-ion battery material using a high-speed segmented detector. Furthermore, it was shown that OBF imaging is usable for real-time imaging, which makes low-dose observations of beam-sensitive materials much easier to achieve.

High contrast STEM imaging for light elements by an annular segmented detector.

Annular bright-field scanning transmission electron microscopy (ABF STEM) has been actively used to directly observe the light element atoms inside materials and devices. However, the detector angle condition for conventional ABF STEM has been empirically selected and thus is not always optimized for observing ultra-light element atoms such as hydrogen and lithium atoms. In this study, the detector conditions for ABF STEM were reexamined by calculating a new type of phase contrast transfer function (PCTF) for an annularly segmented detector to maximize the image contrast of ultra-light element atoms such as lithium. Using this new PCTF, an improved detector geometry for observing lithium atoms is demonstrated, which is confirmed by the image simulations and experiments in several types of lithium cathode materials.