Spatially-resolved Techniques Research Articles

Nanoscale lattice dynamics in hexagonal boron nitride moir\xe9 superlattices

Twisted two-dimensional van der Waals (vdW) heterostructures have unlocked a new means for manipulating the properties of quantum materials. The resulting mesoscopic moiré superlattices are accessible to a wide variety of scanning probes. To date, spatially-resolved techniques have prioritized electronic structure visualization, with lattice response experiments only in their infancy. Here, we therefore investigate lattice dynamics in twisted layers of hexagonal boron nitride (hBN), formed by a minute twist angle between two hBN monolayers assembled on a graphite substrate. Nano-infrared (nano-IR) spectroscopy reveals systematic variations of the in-plane optical phonon frequencies amongst the triangular domains and domain walls in the hBN moiré superlattices. Our first-principles calculations unveil a local and stacking-dependent interaction with the underlying graphite, prompting symmetry-breaking between the otherwise identical neighboring moiré domains of twisted hBN.

Electrolyte-Free Spectroscopy and Imaging of Graphite Intercalation.

Engineering electrode materials for optoelectronic and energy storage applications requires a fundamental understanding of intercalation using spatially-resolved techniques. However, spectroscopic methods can have limited spatial resolution and low intensity since the signal passes through electrolyte. Here, a device geometry is presented in which the electrolyte is laterally separated from the area probed spectroscopically, so that the signal does not pass through the electrolyte. This geometry enables us to visualize ion transport with optical microscopy and monitor charge transfer with Raman and visible reflectance spectroscopies. In addition, vibrational changes are probed in the mid-IR, a region previously difficult to access due to electrolyte absorption. This geometry will allow many layered electrodes to be probed in situ using time- and spatially-resolved techniques, including photon and electron spectroscopies.

Spatially resolved oxygen reaction, water, and temperature distribution: Experimental results as a function of flow field and implications for polymer electrolyte fuel cell operation

In situ and ex situ spatially-resolved techniques are employed to investigate reactant distribution and its impacts in a polymer electrolyte fuel cell. Temperature distribution data provides further evidence for secondary flows inferred from reactant imaging data, highlighting the contribution of convection in heat as well as reactant distribution. Water build-up from neutron tomography is linked to component degradation, matching the pattern seen in the reactant distribution and thus suggesting that high, non-uniform local current densities shape degradation patterns in fuel cells. The correlations shown between different techniques confirm the use of the versatile reactant imaging technique, which is used to compare commonly used flow field designs. Among serpentine-type designs, the single serpentine is superior in both equivalent current density and reactant distribution, showing large contributions from convective flow. On the other hand, the interdigitated design is shown to produce larger equivalent current densities, while showing a somewhat poorer reactant distribution. Considering the correlations drawn between the techniques, this suggests that the interdigitated design compromises durability in favour of power output. The results highlight how established techniques provide a robust background for the use of a new and flexible imaging technique toward designing advanced flow fields for practical fuel cell applications.

Localized segregation of gold in ultrathin Fe films on Au(001)

The growth of up to 10 monolayer-thick Fe films on a Au(001) surface was investigated during deposition at room temperature and during annealing using low-energy electron diffraction and x-ray photoemission spectroscopy as well as locally with low-energy electron microscopy and photoemission electron microscopy. The growth proceeds with a submonolayer of Au segregating to the surface of Fe, which is in agreement with previous studies. Annealing was found to be critical for the presence of Au on the Fe surface. Our findings show that Au segregation proceeds by the formation of cracks in the Fe film, starting at the annealing temperature of 190 {\deg}C, through which Au diffuses towards the surface. We explain the localized Au segregation with a shadowing effect due to the oblique deposition geometry. As a result, an Fe film with significantly improved roughness, but covered with a Au overlayer, is obtained. This study shows the necessity to employ spatially-resolved techniques to fully understand the growth modes of the layered epitaxial systems.

The reversal of the laser-beam-induced-current contrast with varying illumination density in a Cu2ZnSnSe4 thin-film solar cell

We apply an array of correlated spatially-resolved techniques, including μ-Raman/photoluminescence/reflectance/laser-beam-induced-current in conjunction with scanning electron microscopy and atomic force microscopy, to study the impact of the microscopic-scale thickness inhomogeneity of CdS layer in a Cu2ZnSnSe4 thin-film solar cell. Thicker CdS regions are found to cause more light reflecting loss thus yield lower external quantum efficiencies and energy conversion efficiencies than the general area. However, these regions show much less efficiency degradation at high illumination intensity, leading to an inversion of laser-beam-induced-current contrast in the area mapping. While improving the CdS layer uniformity can boost the device performance, the finding further points out the possibility of operating thin-film photovoltaic devices based on the similar materials (such as CuInGaSe2, CdTe, Cu2ZnSn(S,Se)4) under a substantially higher illumination density for concentrated photovoltaic and photo-detection.

A Layered Structure in the Organic Envelopes of the Prismatic Layer of the Shell of the Pearl Oyster Pinctada margaritifera (Mollusca, Bivalvia)

The organic interprismatic layers of the mollusc Pinctada margaritifera are studied using a variety of highly spatially-resolved techniques to establish their composition and structure. Our results show that both the interlamellar sheets of the nacre and interprismatic envelopes form layered structures. Additionally, these organic layers are neither homogeneous in composition, nor continuous in their structure. Both structures play a major role in the biomineralization process and act as a boundary between mineral units.

Organic matter heterogeneities in 2.72 Ga stromatolites: Alteration versus preservation by sulfur incorporation

The stromatolites of the weakly metamorphosed 2.72 Ga Tumbiana Formation present abundant organic globules that resemble in size, shape and distribution the microorganisms observed in modern stromatolites. In order to evaluate the significance of these cell-like organic materials, we characterized organic matter in-situ down to the nanoscale using a combination of Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), Raman microspectroscopy, scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM). These analyses revealed the occurrence of two distinct types of organic matter forming μm-scale textural and chemical heterogeneities distributed in distinct mineralogical laminae of the stromatolites. Type A organic matter, which is by far the most abundant, consists of sulfur-poor organic matter that is located in mud-type laminae at grain boundaries, mostly in association with silicate minerals. In contrast, Type B organic matter is rare and preserved as inclusions in the core of calcite grains forming laminates. It occurs as micrometer-sized cell-like globules containing variable amounts of organic sulfur likely in the form of thiophenes. Different scenarios may account for these compositional heterogeneities in the kerogen. Based on textural and compositional analogies with modern stromatolites, it is argued that Type B sulfur-rich globules may represent microbial cells protected by mineral encapsulation and selectively preserved through polymerization by early diagenetic sulfurization. In modern sediments, this reaction is fuelled by bacterial sulfate reduction (BSR). This metabolism has been widely considered as a major driver in modern stromatolites calcification and could thus have played an important role in the formation of the Tumbiana Formation stromatolites. In contrast, Type A sulfur-poor organic matter corresponds to either fossil extracellular polymer substances (EPS) or recondensed kerogen. This pool was likely not sulfurized due to either local and/or timely variations in the concentrations of H 2S or adverse pyritization driven by the availability of iron. Our observations thus show the need to use spatially-resolved techniques to complement organic geochemistry analyses and provide a detailed analysis of the organic carbon pools composing Archean stromatolites.

GENERATING and MANIPULATING SPINS IN SEMICONDUCTORS

Spin-orbit coupling in semiconductors relates the spin of an electron to its momentum, and provides a pathway for electrically initializing and manipulating electron spins for applications in spintronics and spin-based quantum information processing. This coupling can be regulated with strain in bulk semiconductors and quantum confinement in semiconductor heterostructures. We will provide an overview of optical studies exploring spin dynamics in conventional and magnetic semiconductors, followed by recent experiments probing all-electrical generation and manipulation of spins. Using Faraday and Kerr rotation magneto-optical spectroscopies with temporal and spatial resolution, current-induced spin polarization1 and the spin Hall effect2 have been observed using both spatially-resolved and temporally-resolved techniques in bulk semiconductors. More recently, we have investigated the spin Hall effect and current-induced spin polarization in two-dimensional electron gases confined in (110) AlGaAs quantum wells using Kerr rotation microscopy.3 In marked contrast to previous measurements in three dimensional systems, the spin Hall profile in two dimensions shows a surprisingly complex structure and the current-induced spin polarization is out-of-plane. The experiments map the strong dependence of the current-induced spin polarization to the crystal axis along which the electric field is applied, reflecting the anisotropy of the spin-orbit interaction. The effect of reducing feature sizes in electrical spintronic devices is relevant for future technological applications. To this end, we discuss related measurements probing electron spin dynamics in narrow two-dimensional InGaAs quantum well wires with widths ranging from the micron to the submicron scale.4 The data reveal a surprising slowing of the electron spin relaxation in reduced geometries. These results reveal opportunities for tuning a spin source using quantum confinement, strain and device engineering in non-magnetic materials. This work was supported by the ARO, DARPA, NSF and ONR. Note from Publisher: This article contains the abstract only.

Determining the local coordination of aluminium in cement using electron energy loss near-edge structure

The local site symmetry of aluminium in Al-substituted calcium silicate hydrate phases, similar to those found in hardened Portland cement pastes, has been determined by experimental measurement and theoretical modelling of the electron energy loss near-edge structure associated with the aluminium K-edge measured using parallel electron energy loss spectroscopy in the transmission electron microscope. Changes in the local aluminium environment were observed between different regions of the microstructure which are explained in terms of aluminium substitution into both tetrahedral silicon and octahedral magnesium sites. This spatially-resolved information is in excellent agreement with27Al and29Si magic angle spinning nuclear magnetic resonance data on bulk samples as well as the predictions based upon compositional trends derived from the results of energy dispersive X-ray and electron energy loss elemental microanalysis. In a wider context we wish to stress the complementarity of both spatially-resolved and bulk spectroscopic techniques, which possess differing degrees of sensitivity, in the analysis of materials science samples.