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 Quadrangles Av-11 and Av-12 on Vesta are located at the northern rim of the giant Rheasilvia south polar impact basin. The primary geologic units in Av-11 and Av-12 include material from the Rheasilvia impact basin formation, smooth material and different types of impact crater structures (such as bimodal craters, dark and bright crater ray material and dark ejecta material). Av-11 and Av-12 exhibit almost the full range of mass wasting features observed on Vesta, such as slump blocks, spur-and-gully morphologies and landslides within craters. Processes of collapse, slope instability and seismically triggered events force material to slump down crater walls or scarps and produce landslides or rotational slump blocks. The spur-and-gully morphology that is known to form on Mars is also observed on Vesta; however, on Vesta this morphology formed under dry conditions.

The Ni/NiO core/shell structure is one of the most efficient co-catalysts for solar water splitting when coupled with suitable semiconducting oxides. It has been shown that pretreated Ni/NiO core/shell structures are more active than pure Ni metal, pure NiO or mixed dispersion of Ni metal and NiO nanoparticles. However, Ni/NiO core/shell structures on TiO2 are only able to generate H2 but not O2 in aqueous water. The nature of the hydrogen evolution reaction in these systems was investigated by correlating photochemical H2 production with atomic resolution structure determined with aberration corrected electron microscopy. It was found that the core/shell structure plays an important role for H2 generation but the system undergoes deactivation due to a loss of metallic Ni. During the H2 evolution reaction, the metal core initially formed partial voids which grew and eventually all the Ni diffused out of the core-shell into solution leaving an inactive hollow NiO void structure. The H2 evolution was generated by a photochemical reaction involving photocorrosion of Ni metal.

Asteroids provide fundamental clues to the formation and evolution of planetesimals. Collisional models based on the depletion of the primordial main belt of asteroids predict 10–15 craters >400 km should have formed on Ceres, the largest object between Mars and Jupiter, over the last 4.55 Gyr. Likewise, an extrapolation from the asteroid Vesta would require at least 6–7 such basins. However, Ceres’ surface appears devoid of impact craters >∼280 km. Here, we show a significant depletion of cerean craters down to 100–150 km in diameter. The overall scarcity of recognizable large craters is incompatible with collisional models, even in the case of a late implantation of Ceres in the main belt, a possibility raised by the presence of ammoniated phyllosilicates. Our results indicate that a significant population of large craters has been obliterated, implying that long-wavelength topography viscously relaxed or that Ceres experienced protracted widespread resurfacing.

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an ‘aloof’ electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies <1 eV can be ‘safely’ investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C–H, N–H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope.

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.

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.

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.