ASU Scholarship Showcase

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.

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.

We study the so-called Descent, or [bar over Q], Equation for the null polygonal supersymmetric Wilson loop in the framework of the pentagon operator product expansion. To properly address this problem, one requires to restore the cyclicity of the loop broken by the choice of OPE channels. In the course of the study, we unravel a phenomenon of twist enhancement when passing to a cyclically shifted channel. Currently, we focus on the consistency of the all-order Descent Equation for the particular case relating the NMHV heptagon to MHV hexagon. We find that the equation establishes a relation between contributions of different twists and successfully verify it in perturbation theory making use of available bootstrap predictions for elementary pentagons.

We study event shapes in N = 4SYM describing the angular distribution of energy and R-charge in the final states created by the simplest half-BPS scalar operator. Applying the approach developed in the companion paper arXiv:1309.0769, we compute these observables using the correlation functions of certain components of the N = 4 stress-tensor supermultiplet: the half-BPS operator itself, the R-symmetry current and the stress tensor. We present master formulas for the all-order event shapes as convolutions of the Mellin amplitude defining the correlation function of the half-BPS operators, with a coupling-independent kernel determined by the choice of the observable. We find remarkably simple relations between various event shapes following from N = 4 superconformal symmetry. We perform thorough checks at leading order in the weak coupling expansion and show perfect agreement with the conventional calculations based on amplitude techniques. We extend our results to strong coupling using the correlation function of half-BPS operators obtained from the AdS/CFT correspondence.

We analyze the near-collinear limit of the null polygonal hexagon super Wilson loop in the planar N = 4 super-Yang–Mills theory. We focus on its Grassmann components which are dual to next-to-maximal helicity-violating (NMHV) scattering amplitudes. The kinematics in question is studied within a framework of the operator product expansion that encodes propagation of excitations on the background of the color flux tube stretched between the sides of Wilson loop contour. While their dispersion relation is known to all orders in 't Hooft coupling from previous studies, we find their form factor couplings to the Wilson loop. This is done making use of a particular tessellation of the loop where pentagon transitions play a fundamental role. Being interested in NMHV amplitudes, the corresponding building blocks carry a nontrivial charge under the SU(4) R-symmetry group. Restricting the current consideration to twist-two accuracy, we analyze two-particle contributions with a fermion as one of the constituents in the pair. We demonstrate that these nonsinglet pentagons obey bootstrap equations that possess consistent solutions for any value of the coupling constant. To confirm the correctness of these predictions, we calculate their contribution to the super Wilson loop demonstrating agreement with recent results to four-loop order in 't Hooft coupling.

In this paper we study the four-point correlation function of the energy–momentum supermultiplet in theories with N = 4 superconformal symmetry in four dimensions. We present a compact form of all component correlators as an invariant of a particular abelian subalgebra of the N = 4 superconformal algebra. This invariant is unique up to a single function of the conformal cross-ratios which is fixed by comparison with the correlation function of the lowest half-BPS scalar operators. Our analysis is independent of the dynamics of a specific theory, in particular it is valid in N = 4 super Yang–Mills theory for any value of the coupling constant. We discuss in great detail a subclass of component correlators, which is a crucial ingredient for the recent study of charge-flow correlations in conformal field theories. We compute the latter explicitly and elucidate the origin of the interesting relations among different types of flow correlations previously observed in arXiv:1309.1424.

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.

Novel hydride chemistries are employed to deposit light-emitting Ge_1-y Sn_yalloys with y ≤ 0.1 by Ultra-High Vacuum Chemical Vapor Deposition (UHV-CVD) on Ge-buffered Si wafers. The properties of the resultant materials are systematically compared with similar alloys grown directly on Si wafers. The fundamental difference between the two systems is a fivefold (and higher) decrease in lattice mismatch between film and virtual substrate, allowing direct integration of bulk-like crystals with planar surfaces and relatively low dislocation densities. For y ≤ 0.06, the CVD precursors used were digermane Ge₂H₆ and deuterated stannane SnD₄. For y ≥ 0.06, the Ge precursor was changed to trigermane Ge₃H₈, whose higher reactivity enabled the fabrication of supersaturated samples with the target film parameters. In all cases, the Ge wafers were produced using tetragermane Ge₄H₁₀ as the Ge source. The photoluminescence intensity from Ge_1-y Sn_y /Ge films is expected to increase relative to Ge_1-y Sn_y /Si due to the less defected interface with the virtual substrate. However, while Ge_1-y Sn_y /Si films are largely relaxed, a significant amount of compressive strain may be present in the Ge_1-y Sn_y /Ge case. This compressive strain can reduce the emission intensity by increasing the separation between the direct and indirect edges. In this context, it is shown here that the proposed CVD approach to Ge_1-y Sn_y /Ge makes it possible to approach film thicknesses of about 1  μm, for which the strain is mostly relaxed and the photoluminescence intensity increases by one order of magnitude relative to Ge_1-y Sn_y /Si films. The observed strain relaxation is shown to be consistent with predictions from strain-relaxation models first developed for the Si_1-x Ge_x /Si system. The defect structure and atomic distributions in the films are studied in detail using advanced electron-microscopy techniques, including aberration corrected STEM imaging and EELS mapping of the average diamond–cubic lattice.