Faculty and Staff

The development of non-volatile logic through direct coupling of spontaneous ferroelectric polarization with semiconductor charge carriers is nontrivial, with many issues, including epitaxial ferroelectric growth, demonstration of ferroelectric switching and measurable semiconductor modulation. Here we report a true ferroelectric field effect—carrier density modulation in an underlying Ge(001) substrate by switching of the ferroelectric polarization in epitaxial c-axis-oriented BaTiO₃ grown by molecular beam epitaxy. Using the density functional theory, we demonstrate that switching of BaTiO₃ polarization results in a large electric potential change in Ge. Aberration-corrected electron microscopy confirms BaTiO₃ tetragonality and the absence of any low-permittivity interlayer at the interface with Ge. The non-volatile, switchable nature of the single-domain out-of-plane ferroelectric polarization of BaTiO₃ is confirmed using piezoelectric force microscopy. The effect of the polarization switching on the conductivity of the underlying Ge is measured using microwave impedance microscopy, clearly demonstrating a ferroelectric field effect.

The emission properties of GeSn heterostructure pin diodes have been investigated. The devices contain thick (400–600 nm) Ge_1-y Sn_y i-layers spanning a broad compositional range below and above the crossover Sn concentration y_c where the Ge_1-y Sn_y alloy becomes a direct-gap material. These results are made possible by an optimized device architecture containing a single defected interface thereby mitigating the deleterious effects of mismatch-induced defects. The observed emission intensities as a function of composition show the contributions from two separate trends: an increase in direct gap emission as the Sn concentration is increased, as expected from the reduction and eventual reversal of the separation between the direct and indirect edges, and a parallel increase in non-radiative recombination when the mismatch strains between the structure components is partially relaxed by the generation of misfit dislocations. An estimation of recombination times based on the observed electroluminescence intensities is found to be strongly correlated with the reverse-bias dark current measured in the same devices.

The compositional dependence of the lowest direct and indirect band gaps in Ge_1-ySn_y alloys has been determined from room-temperature photoluminescence measurements. This technique is particularly attractive for a comparison of the two transitions because distinct features in the spectra can be associated with the direct and indirect gaps. However, detailed modeling of these room temperature spectra is required to extract the band gap values with the high accuracy required to determine the Sn concentration y_c at which the alloy becomes a direct gap semiconductor. For the direct gap, this is accomplished using a microscopic model that allows the determination of direct gap energies with meV accuracy. For the indirect gap, it is shown that current theoretical models are inadequate to describe the emission properties of systems with close indirect and direct transitions. Accordingly, an ad hoc procedure is used to extract the indirect gap energies from the data. For y < 0.1 the resulting direct gap compositional dependence is given by ΔE₀ = −(3.57 ± 0.06)y (in eV). For the indirect gap, the corresponding expression is ΔE_ind = −(1.64 ± 0.10)y (in eV). If a quadratic function of composition is used to express the two transition energies over the entire compositional range 0 ≤ y ≤ 1, the quadratic (bowing) coefficients are found to be b₀ = 2.46 ± 0.06 eV (for E0) and b_ind = 1.03 ± 0.11 eV (for E_ind). These results imply a crossover concentration y_c = $0.073 [+0.007 over -0.006], much lower than early theoretical predictions based on the virtual crystal approximation, but in better agreement with predictions based on large atomic supercells.

The Dawn Framing Camera (FC) has imaged the northern hemisphere of the Asteroid (4) Vesta at high spatial resolution and coverage. This study represents the first investigation of the overall geology of the northern hemisphere (22–90°N, quadrangles Av-1, 2, 3, 4 and 5) using these unique Dawn mission observations. We have compiled a morphologic map and performed crater size–frequency distribution (CSFD) measurements to date the geologic units. The hemisphere is characterized by a heavily cratered surface with a few highly subdued basins up to ∼200 km in diameter. The most widespread unit is a plateau (cratered highland unit), similar to, although of lower elevation than the equatorial Vestalia Terra plateau. Large-scale troughs and ridges have regionally affected the surface. Between ∼180°E and ∼270°E, these tectonic features are well developed and related to the south pole Veneneia impact (Saturnalia Fossae trough unit), elsewhere on the hemisphere they are rare and subdued (Saturnalia Fossae cratered unit). In these pre-Rheasilvia units we observed an unexpectedly high frequency of impact craters up to ∼10 km in diameter, whose formation could in part be related to the Rheasilvia basin-forming event. The Rheasilvia impact has potentially affected the northern hemisphere also with S–N small-scale lineations, but without covering it with an ejecta blanket. Post-Rheasilvia impact craters are small (<60 km in diameter) and show a wide range of degradation states due to impact gardening and mass wasting processes. Where fresh, they display an ejecta blanket, bright rays and slope movements on walls. In places, crater rims have dark material ejecta and some crater floors are covered by ponded material interpreted as impact melt.

Oppia Quadrangle Av-10 (288–360°E, ±22°) is a junction of key geologic features that preserve a rough history of Asteroid (4) Vesta and serves as a case study of using geologic mapping to define a relative geologic timescale. Clear filter images, stereo-derived topography, slope maps, and multispectral color-ratio images from the Framing Camera on NASA’s Dawn spacecraft served as basemaps to create a geologic map and investigate the spatial and temporal relationships of the local stratigraphy. Geologic mapping reveals the oldest map unit within Av-10 is the cratered highlands terrain which possibly represents original crustal material on Vesta that was then excavated by one or more impacts to form the basin Feralia Planitia. Saturnalia Fossae and Divalia Fossae ridge and trough terrains intersect the wall of Feralia Planitia indicating that this impact basin is older than both the Veneneia and Rheasilvia impact structures, representing Pre-Veneneian crustal material. Two of the youngest geologic features in Av-10 are Lepida (∼45 km diameter) and Oppia (∼40 km diameter) impact craters that formed on the northern and southern wall of Feralia Planitia and each cross-cuts a trough terrain. The ejecta blanket of Oppia is mapped as ‘dark mantle’ material because it appears dark orange in the Framing Camera ‘Clementine-type’ color-ratio image and has a diffuse, gradational contact distributed to the south across the rim of Rheasilvia. Mapping of surface material that appears light orange in color in the Framing Camera ‘Clementine-type’ color-ratio image as ‘light mantle material’ supports previous interpretations of an impact ejecta origin. Some light mantle deposits are easily traced to nearby source craters, but other deposits may represent distal ejecta deposits (emplaced >5 crater radii away) in a microgravity environment.

We used Dawn spacecraft data to identify and delineate geological units and landforms in the Marcia quadrangle of Vesta as a means to assess the role of the large, relatively young impact craters Marcia (∼63 km diam.) and Calpurnia (∼53 km diam.) and their surrounding ejecta field on the local geology. We also investigated a local topographic high with a dark-rayed crater named Aricia Tholus, and the impact crater Octavia that is surrounded by a distinctive diffuse mantle. Crater counts and stratigraphic relations suggest that Marcia is the youngest large crater on Vesta, in which a putative impact melt on the crater floor ranges in age between ∼40 and 60 Ma (depending upon choice of chronology system), and Marcia’s ejecta blanket ranges in age between ∼120 and 390 Ma (depending upon choice of chronology system).

We interpret the geologic units in and around Marcia crater to mark a major vestan time-stratigraphic event, and that the Marcia Formation is one of the geologically youngest formations on Vesta. Marcia crater reveals pristine bright and dark material in its walls and smooth and pitted terrains on its floor. The smooth unit we interpret as evidence of flow of impact melts and (for the pitted terrain) release of volatiles during or after the impact process. The distinctive dark ejecta surrounding craters Marcia and Calpurnia is enriched in OH- or H-bearing phases and has a variable morphology, suggestive of a complex mixture of impact ejecta and impact melts including dark materials possibly derived from carbonaceous chondrite-rich material. Aricia Tholus, which was originally interpreted as a putative vestan volcanic edifice based on lower resolution observations, appears to be a fragment of an ancient impact basin rim topped by a dark-rayed impact crater. Octavia crater has a cratering model formation age of ∼280–990 Ma based on counts of its ejecta field (depending upon choice of chronology system), and its ejecta field is the second oldest unit in this quadrangle. The relatively young craters and their related ejecta materials in this quadrangle are in stark contrast to the surrounding heavily cratered units that are related to the billion years old or older Rheasilvia and Veneneia impact basins and Vesta’s ancient crust preserved on Vestalia Terra.

We studied high-resolution images of asteroid Vesta's surface (~70 and 20–25 m/pixel) obtained during the High- and Low-Altitude Mapping Orbits (HAMO, LAMO) of NASA's Dawn mission to assess the formation mechanisms responsible for a variety of lobate, flow-like features observed across the surface. We searched for evidence of volcanic flows, based on prior mathematical modeling and the well-known basaltic nature of Vesta's crust, but no unequivocal morphologic evidence of ancient volcanic activity has thus far been identified. Rather, we find that all lobate, flow-like features on Vesta appear to be related either to impact or erosional processes. Morphologically distinct lobate features occur in and around impact craters, and most of these are interpreted as impact ejecta flows, or possibly flows of impact melt. Estimates of melt production from numerical models and scaling laws suggests that large craters like Marcia (~60 km diameter) could have potentially produced impact melt volumes ranging from tens of millions of cubic meters to a few tens of cubic kilometers, which are relatively small volumes compared to similar-sized lunar craters, but which are consistent with putative impact melt features observed in Dawn images. There are also examples of lobate flows that trend downhill both inside and outside of crater rims and basin scarps, which are interpreted as the result of gravity-driven mass movements (slumps and landslides).

Earth-abundant sustainable inorganic thin-film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Herein, the earth-abundant solar cell device, Cu₂ZnSnS_(4-x)Se_x, is reported, which shows a high abundance of secondary phases compared to similarly grown Cu₂ZnSnSe₄.

We present two-dimensional Mg(OH)₂ sheets and their vertical heterojunctions with CVD-MoS₂ for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)₂ sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)₂ have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)₂ is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)₂ sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)₂ sheets together with CVD-MoS₂ in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS₂ sheets to Mg(OH)₂, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)₂, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.

Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS₃) whiskers are made out of weakly interacting TiS₃ layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS₃ both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS₃ have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the A_g^S-S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS₃ with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.