Olivine Crystal Structure-Directed Twinning in Iron Germanium Sulfide (Fe2GeS4) Nanoparticles.

Understanding the microstructure of complex crystal structures is critical for controlling material properties in next-generation devices. Synthetic reports of twinning in bulk and nanostructured crystals with detailed crystallographic characterization are integral for advancing systematic studies of twinning phenomena. Herein, we report a synthetic route to controllably twinned olivine nanoparticles. Microstructural characterization of Fe2GeS4 nanoparticles via electron microscopy (imaging, diffraction, and crystallographic analysis) demonstrates the formation of triplets of twins, or trillings. We establish synthetic control over the particle crystallinity and crystal growth. We describe the geometrical basis for twin formation, hexagonal pseudosymmetry of the orthorhombic lattice, and rank all of the reported olivine compounds according to this favorability to form twins. The work in this study highlights an area ripe for future exploration with respect to the advancement of solution-phase synthetic approaches that can control microstructure in compositionally complex, technologically relevant structures. Finally, we discuss the potential implications for olivine properties and performance in various applications.

Comparison of convergent beam electron diffraction and annular bright field atomic imaging for GaN polarity determination.

A comparison of two electron microscopy techniques used to determine the polarity of GaN nanowires is presented. The techniques are convergent beam electron diffraction (CBED) in TEM mode and annular bright field (ABF) imaging in aberration corrected STEM mode. Both measurements were made at nominally the same locations on a variety of GaN nanowires. In all cases the two techniques gave the same polarity result. An important aspect of the study was the calibration of the CBED pattern rotation relative to the TEM image. Three different microscopes were used for CBED measurements. For all three instruments there was a substantial rotation of the diffraction pattern (120 or 180°) relative to the image, which, if unaccounted for, would have resulted in incorrect polarity determination. The study also shows that structural defects such as inversion domains can be readily identified by ABF imaging, but may escape identification by CBED. The relative advantages of the two techniques are discussed.

In-Depth View of the Structure and Growth of SnO2 Nanowires and Nanobrushes.

Strategic application of an array of complementary imaging and diffraction techniques is critical to determine accurate structural information on nanomaterials, especially when also seeking to elucidate structure-property relationships and their effects on gas sensors. In this work, SnO2 nanowires and nanobrushes grown via chemical vapor deposition (CVD) displayed the same tetragonal SnO2 structure as revealed via powder X-ray diffraction bulk crystallinity data. Additional characterization using a range of electron microscopy imaging and diffraction techniques, however, revealed important structure and morphology distinctions between the nanomaterials. Tailoring scanning transmission electron microscopy (STEM) modes combined with transmission electron backscatter diffraction (t-EBSD) techniques afforded a more detailed view of the SnO2 nanostructures. Indeed, upon deeper analysis of individual wires and brushes, we discovered that, despite a similar bulk structure, wires and brushes grew with different crystal faces and lattice spacings. Had we not utilized multiple STEM diffraction modes in conjunction with t-EBSD, differences in orientation related to bristle density would have been overlooked. Thus, it is only through a methodical combination of several structural analysis techniques that precise structural information can be reliably obtained.

Contact mechanics and tip shape in AFM-based nanomechanical measurements.

Stiffness-load curves obtained in quantitative atomic force acoustic microscopy (AFAM) measurements depend on both the elastic properties of the sample and the geometry of the atomic force microscope (AFM) tip. The geometry of silicon AFM tips changes when used in contact mode, affecting measurement accuracy. To study the influence of tip geometry, we subjected ten AFM tips to the same series of AFAM measurements. Changes in tip shape were observed in the scanning electron microscope (SEM) between individual AFAM tests. Because all of the AFAM measurements were performed on the same sample, variations in AFAM stiffness-load curves were attributed to differences in tip geometry. Contact-mechanics models that assumed simple tip geometries were used to analyze the AFAM data, but the calculated values for tip dimensions did not agree with those provided by SEM images. Therefore, we used a power-law approach that allows for a nonspherical tip geometry. We found that after several AFAM measurements, the geometry of the tips at the very end is intermediate between those of a flat punch and a hemisphere. These results indicate that the nanoscale tip-sample contact cannot easily be described in terms of simple, ideal geometries.