Jeffrey Ditto

Rational design of efficient electrode-electrolyte interfaces for solid-state energy storage using ion soft landing.

The rational design of improved electrode–electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly dispersed discrete redox-active cluster anions (50 ng of pure ∼0.75 nm size molybdenum polyoxometalate (POM) anions on 25 μg (∼0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft landing (SL). Electron microscopy provides atomically resolved images of a uniform distribution of individual POM species soft landed directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.

Weathering Rinds: Archives of Paleoenvironments on Mount Kenya, East Africa

Weathering-rind thicknesses on pebble- and cobble-size sediment have been used for the past half-century, at least, as an age indicator of postdepositional time following a geologic event. In mountainous terrain, rind thickness is taken as a measurement of weathering over time frames of 0.5 m.yr.; variable thicknesses are used to discriminate relative ages of glacial deposits. The effects of chemical and physical weathering that together produce rinds are only rarely considered, and most research objectives have centered on lichen alteration of clast surfaces. Recent microscopic analyses of weathering rinds on volcanic clasts of ∼70.0-ka to ∼2.0-m.yr. age produced new data on weathering products as well as unexpected incorporated biotic materials undergoing diagenesis. The question as to how much physical/mineral/chemical/biotic paleoenvironmental data might be archived in rinds is discussed. The character and classification of organic materials undergoing diagenesis are also discussed.

Influence of defects on the charge density wave of ([SnSe]1+δ)1(VSe2)1 ferecrystals

A series of ferecrystalline compounds ([SnSe]1+δ)1(VSe2)1 with varying Sn/V ratios were synthesized using the modulated elemental reactant technique. Temperature-dependent specific heat data reveal a phase transition at 102 K, where the heat capacity changes abruptly. An abrupt increase in electrical resistivity occurs at the same temperature, correlated with an abrupt increase in the Hall coefficient. Combined with the magnitude and nature of the specific heat discontinuity, this suggests that the transition is similar to the charge density wave transitions in transition metal dichalcogenides. An ordered intergrowth was formed over a surprisingly wide compositional range of Sn/V ratios of 0.89 ≤ 1 + δ ≤ 1.37. X-ray diffraction and transmission electron microscopy reveal the formation of various volume defects in the compounds in response to the nonstoichiometry. The electrical resistivity and Hall coefficient data of samples with different Sn/V ratios show systematic variation in the carrier concentration with the Sn/V ratio. There is no significant change in the onset temperature of the charge density wave transition, only a variation in the carrier densities before and after the transition. Given the sensitivity of the charge density wave transitions of transition metal dichalcogenides to variations in composition, it is very surprising that the charge density wave transition observed at 102 K for ([SnSe]1.15)1(VSe2)1 is barely influenced by the nonstoichiometry and structural defects. This might be a consequence of the two-dimensional nature of the structurally independent VSe2 layers.

Designed Synthesis of van der Waals Heterostructures: The Power of Kinetic Control.

Selecting specific 2D building blocks and specific layering sequences of van der Waals heterostructures should allow the formation of new materials with designed properties for specific applications. Unfortunately, the synthetic ability to prepare such structures at will, especially in a manner that can be manufactured, does not exist. Herein, we report the targeted synthesis of new metal-semiconductor heterostructures using the modulated elemental-reactant technique to nucleate specific 2D building blocks, control their thickness, and avoid epitaxial structures with long-range order. The building blocks, VSe2 and GeSe2 , have different crystal structures, which inhibits cation intermixing. The precise control of this approach enabled us to synthesize heterostructures containing GeSe2 monolayers alternating with VSe2 structural units with specific sequences. The transport properties systematically change with nanoarchitecture and a charge-density wave-like transition is observed.

Amorphous Mixed-Metal Oxide Thin Films from Aqueous Solution Precursors with Near-Atomic Smoothness

Thin films with tunable and homogeneous composition are required for many applications. We report the synthesis and characterization of a new class of compositionally homogeneous thin films that are amorphous solid solutions of Al2O3 and transition metal oxides (TMOx) including VOx, CrOx, MnOx, Fe2O3, CoOx, NiO, CuOx, and ZnO. The synthesis is enabled by the rapid decomposition of molecular transition-metal nitrates TM(NO3)x at low temperature along with precondensed oligomeric Al(OH)x(NO3)3-x cluster species, both of which can be processed from aq solution. The films are dense, ultrasmooth (Rrms < 1 nm, near 0.1 nm in many cases), and atomically mixed amorphous metal-oxide alloys over a large composition range. We assess the chemical principles that favor the formation of amorphous homogeneous films over rougher phase-segregated nanocrystalline films. The synthesis is easily extended to other compositions of transition and main-group metal oxides. To demonstrate versatility, we synthesized amorphous V0.1Cr0.1Mn0.1Fe0.1Zn0.1Al0.5Ox and V0.2Cr0.2Fe0.2Al0.4Ox with Rrms ≈ 0.1 nm and uniform composition. The combination of ideal physical properties (dense, smooth, uniform) and broad composition tunability provides a platform for film synthesis that can be used to study fundamental phenomena when the effects of transition metal cation identity, solid-state concentration of d-electrons or d-states, and/or crystallinity need to be controlled. The new platform has broad potential use in controlling interfacial phenomena such as electron transfer in solar-cell contacts or surface reactivity in heterogeneous catalysis.

Revisiting Alexander von Humboldt’s Initiation of Rock Coating Research

Secondary, backscattered, high-resolution transmission, and energy-dispersive spectroscopy tools of electron microscopy reexamined Alexander von Humboldt’s field site of “brownish black crust[s]” covering rocks along cataracts of the Orinoco River. Modern tools confirm eighteenth-century analysis that the basic composition includes an abundance of manganese, iron, and carbon. Additional major constituents include clay minerals, calcium, and sometimes barium and cobalt. Backscattered and secondary electron imaging confirms the 2-century-old hypothesis of an accretionary nature of the Orinoco coating. The remarkable Orinoco sheen is produced by a smooth lamellate micromorphology and high concentrations of manganese—the same conditions required to produce lustrous varnishes formed in warm deserts. Although von Humboldt deduced, and we agree, that coating constituents must derive from the Orinoco, electron microscope observations of Mn-enriched diatom fragments, Mn-enriched cocci-bacterial forms, and microstromatolitic textures suggests a role for microorganisms in the 60- to 70-times enhancement of Mn over Fe in these varnishes. With the retrospect of 2 centuries of scholarship, Alexander von Humboldt rightfully deserves to be considered the father of rock coating research.

Modifying a charge density wave transition by modulation doping: ferecrystalline compounds ([Sn1−xBixSe]1.15)1(VSe2)1 with 0 ≤ x ≤ 0.66

A series of alloyed ferecrystals ([Sn1−xBixSe]1.15)1(VSe2)1 with 0 ≤ x ≤ 0.66 was synthesized via the modulated elemental reactants technique. X-ray diffraction of the compounds reveals systematic changes of the lattice parameter and the intensities of the Bragg peaks confirming the successful alloying of the compounds corroborated by Rietveld refinements. Interestingly, both constituents of the intergrowth compounds exhibit systematic structural changes as a function of the Bi-content indicating interlayer interaction. The a-axis lattice parameter of the VSe2 layer expands with increasing Bi-content, which signifies changes in the electronic structure of this constituent. Electrical resistivities, Hall and Seebeck coefficients of compounds with a varying Bi-content present a complex scenario. At low Bi-contents an enhancement of the charge density wave transition is observed, whereas further substitution results in a suppression of the effect. At Bi-contents exceeding x = 0.55 minority carriers from the Sn1−xBixSe layer contribute to the transport properties.

Application of HAADF STEM image analysis to structure determination in rotationally disordered and amorphous multilayered films

We report results from high angle annular dark field scanning transmission electron microscopy (HAADF STEM) image analysis of complex semi-crystalline and amorphous materials, and apply the insights gained from local structure information towards global structure determination. Variations in HAADF STEM intensities for a rotationally disordered heterostructure and an amorphous oxide film are statistically analyzed to extract information regarding the inhomogeneity of the films perpendicular to the substrate. By assuming chemical homogeneity in the film axis parallel to the substrate, the signal intensity variation parallel to the substrate is used to estimate the signal noise level, allowing evaluation of the significance of intensity differences in the substrate normal direction. The positions of HAADF STEM intensity peaks in the perpendicular direction, averaged from multiple images, provide a valuable initial model for a Rietveld refinement of the global c-axis structure of the heterostructure. For an amorphous multi-coat solution-cast oxide sample, the analysis reveals statistically significant variations in the HAADF STEM intensity profile perpendicular to the substrate. These variations indicate an inhomogeneous density profile, presumably related to the spin-casting of individual layers and have implications for understanding the chemical interactions that occur between layers when preparing multilayer amorphous oxide films from solution.

Antiphase Boundaries in the Turbostratically Disordered Misfit Compound (BiSe)(1+δ)NbSe2.

(BiSe)(1+δ)NbSe2 ferecrystals were synthesized in order to determine whether structural modulation in BiSe layers, characterized by periodic antiphase boundaries and Bi-Bi bonding, occurs. Specular X-ray diffraction revealed the formation of the desired compound with a c-axis lattice parameter of 1.21 nm from precursors with a range of initial compositions and initial periodicities. In-plane X-ray diffraction scans could be indexed as hk0 reflections of the constituents, with a rectangular basal BiSe lattice and a trigonal basal NbSe2 lattice. Electron micrographs showed extensive turbostratic disorder in the samples and the presence of periodic antiphase boundaries (approximately 1.5 nm periodicity) in BiSe layers oriented with the [110] direction parallel to the zone axis of the microscope. This indicates that the structural modulation in the BiSe layers is not due to coherency strain resulting from commensurate in-plane lattices. Electrical transport measurements indicate that holes are the dominant charge carrying species, that there is a weak decrease in resistivity as temperature decreases, and that minimal charge transfer occurs from the BiSe to NbSe2 layers. This is consistent with the lack of charge transfer from the BiX to the TX2 layers reported in misfit layer compounds where antiphase boundaries were observed. This suggests that electronic considerations, i.e., localization of electrons in the Bi-Bi pairs at the antiphase boundaries, play a dominant role in stabilizing the structural modulation.

Localized Grounding, Excavation, and Dissection Using In‐Situ Probe Techniques for Focused Ion Beam and Scanning Electron Microscopy: Experiments With Rock Varnish

While investigating rock varnish, we explored novel uses for an in-situ micromanipulator, including charge collection, sample manipulation, as well as digging and dissection at the micron level. Dual-beam focused ion beam microscopes (DB-FIB or FIBSEM) equipped with micromanipulators have proven to be valuable tools for material science, semiconductor research, and product failure analysis. Researchers in many other disciplines utilize the DB-FIB and micromanipulator for site-specific transmission electron microscope (TEM) foil preparation. We have demonstrated additional applications for in-situ micromanipulators.