Untangling competition between epitaxial strain and growth stress through examination of variations in local oxidation.

Understanding corrosion mechanisms is of importance for reducing the global cost of corrosion. While the properties of engineering components are considered at a macroscopic scale, corrosion occurs at micro or nano scale and is influenced by local microstructural variations inherent to engineering alloys. However, studying such complex microstructures that involve multiple length scales requires a multitude of advanced experimental procedures. Here, we present a method using correlated electron microscopy techniques over a range of length scales, combined with crystallographic modelling, to provide understanding of the competing mechanisms that control the waterside corrosion of zirconium alloys. We present evidence for a competition between epitaxial strain and growth stress, which depends on the orientation of the substrate leading to local variations in oxide microstructure and thus protectiveness. This leads to the possibility of tailoring substrate crystallographic textures to promote stress driven, well-oriented protective oxides, and so to improving corrosion performance.

Novel Methods for Recording Stress-Strain Curves in Proton Irradiated Material.

Proton irradiation is often used as a proxy for neutron irradiation but the irradiated layer is typically <50 µm deep; this presents a problem when trying to obtain mechanical test data as a function of irradiation level. Two novel methodologies have been developed to record stress-strain curves for thin proton-irradiated surface layers of SA-508-4N ferritic steel. In the first case, in-situ loading experiments are carried out using a combination of X-ray diffraction and digital image correlation on the near surface region in order to measure stress and strain, thereby eliminating the influence of the non-irradiated volume. The second approach is to manufacture small-scale tensile specimens containing only the proton irradiated volume but approaching the smallest representative volume of the material. This is achieved by high-speed focused ion beam (FIB) milling though the application of a Xe+ Plasma-FIB (PFIB). It is demonstrated that both techniques are capable of recording the early stage of uniaxial flow behaviour of the irradiated material with sufficient accuracy providing a measure of irradiation-induced shift of yield strength, strain hardening and tensile strength.

Ultra-thin van der Waals crystals as semiconductor quantum wells.

Control over the quantization of electrons in quantum wells is at the heart of the functioning of modern advanced electronics; high electron mobility transistors, semiconductor and Capasso terahertz lasers, and many others. However, this avenue has not been explored in the case of 2D materials. Here we apply this concept to van der Waals heterostructures using the thickness of exfoliated crystals to control the quantum well dimensions in few-layer semiconductor InSe. This approach realizes precise control over the energy of the subbands and their uniformity guarantees extremely high quality electronic transport in these systems. Using tunnelling and light emitting devices, we reveal the full subband structure by studying resonance features in the tunnelling current, photoabsorption and light emission spectra. In the future, these systems could enable development of elementary blocks for atomically thin infrared and THz light sources based on intersubband optical transitions in few-layer van der Waals materials.

Indirect to Direct Gap Crossover in Two-Dimensional InSe Revealed by Angle-Resolved Photoemission Spectroscopy.

Atomically thin films of III-VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductors that feature a strong variation of their band gap as a function of the number of layers in the crystal and, specifically for InSe, an expected crossover from a direct gap in the bulk to a weakly indirect band gap in monolayers and bilayers. Here, we apply angle-resolved photoemission spectroscopy with submicrometer spatial resolution (µARPES) to visualize the layer-dependent valence band structure of mechanically exfoliated crystals of InSe. We show that for one-layer and two-layer InSe the valence band maxima are away from the Γ-point, forming an indirect gap, with the conduction band edge known to be at the Γ-point. In contrast, for six or more layers the band gap becomes direct, in good agreement with theoretical predictions. The high-quality monolayer and bilayer samples enable us to resolve, in the photoluminescence spectra, the band-edge exciton (A) from the exciton (B) involving holes in a pair of deeper valence bands, degenerate at Γ, with a splitting that agrees with both µARPES data and the results of DFT modeling. Due to the difference in symmetry between these two valence bands, light emitted by the A-exciton should be predominantly polarized perpendicular to the plane of the two-dimensional crystal, which we have verified for few-layer InSe crystals.

Scalable Patterning of Encapsulated Black Phosphorus.

Atomically thin black phosphorus (BP) has attracted considerable interest due to its unique properties, such as an infrared band gap that depends on the number of layers and excellent electronic transport characteristics. This material is known to be sensitive to light and oxygen and degrades in air unless protected with an encapsulation barrier, limiting its exploitation in electrical devices. We present a new scalable technique for nanopatterning few layered BP by direct electron beam exposure of encapsulated crystals, achieving a spatial resolution down to 6 nm. By encapsulating the BP with single layer graphene or hexagonal boron nitride (hBN), we show that a focused electron probe can be used to produce controllable local oxidation of BP through nanometre size defects created in the encapsulation layer by the electron impact. We have tested the approach in the scanning transmission electron microscope (STEM) and using industry standard electron beam lithography (EBL). Etched regions of the BP are stabilized by a thin passivation layer and demonstrate typical insulating behavior as measured at 300 and 4.3 K. This new scalable approach to nanopatterning of thin air sensitive crystals has the potential to facilitate their wider use for a variety of sensing and electronics applications.

Identifying suboxide grains at the metal-oxide interface of a corroded Zr-1.0%Nb alloy using (S)TEM, transmission-EBSD and EELS.

Here we report a methodology combining TEM, STEM, Transmission-EBSD and EELS to analyse the structural and chemical properties of the metal-oxide interface of corroded Zr alloys in unprecedented detail. TEM, STEM and diffraction results revealed the complexity of the distribution of suboxide grains at the metal-oxide interface. EELS provided accurate quantitative analysis of the oxygen concentration across the interface, identifying the existence of local regions of stoichiometric ZrO and Zr3O2 with varying thickness. Transmission-EBSD confirmed that the suboxide grains can be indexed with the hexagonal ZrO structure predicted with ab initio by Nicholls et al. (2014). The t-EBSD analysis has also allowed for the mapping of a relatively large region of the metal-oxide interface, revealing the location and size distribution of the suboxide grains.