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.
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 resonance force microscopy is used during AFM scanning to resolve instantaneous and progressive nanometer‐scale changes in the contact radius between an AFM tip and a silicon substrate. ...High‐resolution quantitative measurements of contact radius reveal real‐time information on wear rate, fracture, and tip‐symmetry.
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.
We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme ...into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen–gold interactions. Close spatial coupling allows electron delocalization between the nanoparticle cores. The resulting assemblies thus possess optical and electronic properties that emerge as a result of assembly.
Stratocumulus clouds over the Southern Ocean have fewer droplets and are more likely to exist in the predominately supercooled phase than clouds at similar temperatures over northern oceans. One ...likely reason is that this region has few continental and anthropogenic sources of cloud‐nucleating particles that can form droplets and ice. In this work, we present an overview of aerosol particle types over the Southern Ocean, including new measurements made below, in and above clouds in this region. These measurements and others indicate that biogenic sulfur‐based particles >0.1 μm diameter contribute the majority of cloud condensation nuclei number concentrations in summer. Ice nucleating particles tend to have more organic components, likely from sea‐spray. Both types of cloud nucleating particles may increase in a warming climate likely to have less sea ice, more phytoplankton activity, and stronger winds over the Southern Ocean near Antarctica. Taken together, clouds over the Southern Ocean may become more reflective and partially counter the region's expected albedo decrease due to diminishing sea ice. However, detailed modeling studies are needed to test this hypothesis due to the complexity of ocean‐cloud‐climate feedbacks in the region.
Plain Language Summary
Clouds over the Southern Ocean tend to have less droplets and ice crystals than similar clouds over northern oceans due to fewer sources of cloud‐nucleating aerosol particles in the region. In this work, we present an overview of aerosol particle types over the Southern Ocean, including new measurements made below, in and above clouds. These measurements indicate that while sea‐spray‐derived salts do provide cloud nuclei, the majority of aerosol particles that influence summertime clouds in this region are biogenic—that is, derived from ocean microorganisms, with the ocean region near Antarctica being a large summertime source. These cloud‐nucleating particles may increase in a warming climate likely to have less sea ice and more phytoplankton activity near Antarctica. These additional particles could make low clouds reflect more light and offset a portion of the warming expected due to diminishing sea ice in a future climate.
Key Points
Biogenic sulfate dominates the number concentration of 0.1–0.5 microns diameter particles and cloud condensation nuclei (CCN) over the summertime Southern Ocean
Biogenic organics are a key component of ice nucleating particles over the Southern Ocean
As Antarctic climate changes, increased biological activity could partially offset warming effects of sea‐ice loss via influences on CCN
The structure of Co/Pd multilayers has a strong effect on the localized anisotropy distribution within a film and on the resulting switching properties of nanostructures fabricated from identical ...material. By varying the underlying seed layer in sputtered films, the microstructure can be controlled from being highly (111) textured to having a random grain orientation. We find a strong correlation between the lateral homogeneity of grain orientations and the localized anisotropy distribution in the material. X-ray diffraction and reflectivity indicate that the interface is better defined and more uniform in the textured case, consistent with the presence of a strong interfacelike anisotropy.
Wildfires in the western United States are large sources of particulate matter, and the area burned by wildfires is predicted to increase in the future. Some particles released from wildfires can ...affect cloud formation by serving as ice‐nucleating particles (INPs). INPs have numerous impacts on cloud radiative properties and precipitation development. Wildfires are potentially important sources of INPs, as indicated from previous measurements, but their abundance in the free troposphere has not been quantified. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen campaign sampled free tropospheric immersion‐freezing INPs from smoke plumes near their source and downwind, along with widespread aged smoke. The results indicate an enhancement of INPs in smoke plumes relative to out‐of‐plume background air, but the magnitude of enhancement was both temperature and fire dependent. The majority of INPs were inferred to be predominately organic in composition with some contribution from biological sources at modest super cooling, and contributions from minerals at deeper super cooling. A fire involving primarily sagebrush shrub land and aspen forest fuels had the highest INP concentrations measured in the campaign, which is partially attributed to the INP characteristics of lofted, uncombusted plant material. Electron microscopy analysis of INPs also indicated tar balls present in this fire. Parameterization of the plume INP data on a per‐unit‐aerosol surface area basis confirmed that smoke is not an efficient source of INPs. Nevertheless, the high numbers of particles released from, and ubiquity of western US wildfires in summertime, regionally elevate INP concentrations in the free troposphere.
Key Points
Wildfires are sources of ice‐nucleating particles (INPs) to the free troposphere
INP compositions from sampled wildfires were dominated by organics
Contributions of tar ball composition INPs evidenced a secondary formation mechanism
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