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The exotic internal structure of polar topologies in multi-ferroic materials offers a rich landscape for materials science research. As the spatial scale of these entities are often sub-atomic in nature, aberration corrected transmission electron microscopy (TEM) is the ideal characterisation technique. Software to quantify and visualise the slight shifts in atomic placement within unit cells is of paramount importance due to the now routine acquisition of images at such resolution. In the previous ~decade since the commercialisation of aberration corrected TEM, many research groups have written their own code to visualise these polar entities. More recently, open access Python packages have been developed for the purpose of TEM atomic position quantification. Building on these packages, we introduce the TEMUL Toolkit: a Python package for analysis and visualisation of atomic resolution images. Here, we focus specifically on the TopoTEM module of the toolkit where we show an easy to follow, streamlined version of calculating the atomic displacements relative to the surrounding lattice and thus polarisation plotting. We hope this toolkit will benefit the rapidly expanding field of topology based nano-electronic and quantum materials research, and we invite the electron microscopy community to contribute to this open access project., 22 pages, 9 figures

New semiconducting materials, such as state-of-the-art alloys, engineered composites and allotropes of well-established materials can demonstrate unique physical properties and generate wide possibilities for a vast range of applications. Here we demonstrate, for the first time, the fabrication of a metastable allotrope of Ge, tetragonal germanium (ST12-Ge), in nanowire form. Nanowires were grown in a solvothermal-like single-pot method using supercritical toluene as a solvent, at moderate temperatures (290–330 °C) and a pressure of ∼48 bar. One-dimensional (1D) nanostructures of ST12-Ge were achieved via a self-seeded vapour–liquid–solid (VLS)-like paradigm, with the aid of an in situ formed amorphous carbonaceous layer. The ST12 phase of Ge nanowires is governed by the formation of this carbonaceous structure on the surface of the nanowires and the creation of Ge–C bonds. The crystalline phase and structure of the ST12-Ge nanowires were confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The nanowires produced displayed a high aspect ratio, with a very narrow mean diameter of 9.0 ± 1.4 nm, and lengths beyond 4 μm. The ST12-Ge nanowire allotrope was found to have a profound effect on the intensity of the light emission and the directness of the bandgap, as confirmed by a temperature-dependent photoluminescence study.

Recently, electrically conducting heterointerfaces between dissimilar band-insulators (such as lanthanum aluminate and strontium titanate) have attracted considerable research interest. Charge transport has been thoroughly explored and fundamental aspects of conduction firmly established. Perhaps surprisingly, similar insights into conceptually much simpler conducting homointerfaces, such as the domain walls that separate regions of different orientations of electrical polarisation within the same ferroelectric band-insulator, are not nearly so well-developed. Addressing this disparity, we herein report magnetoresistance in approximately conical 180o charged domain walls, which occur in partially switched ferroelectric thin film single crystal lithium niobate. This system is ideal for such measurements: firstly, the conductivity difference between domains and domain walls is extremely and unusually large (a factor of at least 1013) and hence currents driven through the thin film, between planar top and bottom electrodes, are overwhelmingly channelled along the walls; secondly, when electrical contact is made to the top and bottom of the domain walls and a magnetic field is applied along their cone axes (perpendicular to the thin film surface), then the test geometry mirrors that of a Corbino disc, which is a textbook arrangement for geometric magnetoresistance measurement. Our data imply carriers at the domain walls with extremely high room temperature Hall mobilities of up to ~ 3,700cm2V-1s-1. This is an unparalleled value for oxide interfaces (and for bulk oxides too) and is most comparable to mobilities in other systems typically seen at cryogenic, rather than at room, temperature., Comment: 22 pages main text, 24 pages supplementary information. Published in advanced materials, DOI:https://doi.org/10.1002/adma.202204298

Workflows have been developed in the past decade to enable atom probe tomography analysis at cryogenic temperatures. The inability to control the local deposition of the metallic precursor from the gas-injection system (GIS) at cryogenic temperatures makes the preparation of site-specific specimens by using lift-out extremely challenging in the focused-ion beam. Schreiber et al. exploited redeposition to weld the lifted-out sample to a support. Here, we build on their approach to attach the region-of-interest and additionally strengthen the interface with locally sputtered metal from the micromanipulator. Following standard focused-ion beam annular milling, we demonstrate atom probe analysis of Si in both laser pulsing and voltage mode, with comparable analytical performance as a presharpened microtip coupon. Our welding approach is versatile, as various metals could be used for sputtering, and allows similar flexibility as the GIS in principle.

Ge1–xSnx nanowires incorporating a large amount of Sn would be useful for mobility enhancement in nanoelectronic devices, a definitive transition to a direct bandgap for application in optoelectronic devices and to increase the efficiency of the GeSn-based photonic devices. Here we report the catalytic bottom-up fabrication of Ge1–xSnx nanowires with very high Sn incorporation (x > 0.3). These nanowires are grown in supercritical toluene under high pressure (21 MPa). The introduction of high pressure in the vapor–liquid–solid (VLS) like growth regime resulted in a substantial increase of Sn incorporation in the nanowires, with a Sn content ranging between 10 and 35 atom %. The incorporation of Sn in the nanowires was found to be inversely related to nanowire diameter; a high Sn content of 35 atom % was achieved in very thin Ge1–xSnx nanowires with diameters close to 20 nm. Sn was found to be homogeneously distributed throughout the body of the nanowires, without apparent clustering or segregation. The large inclusion of Sn in the nanowires could be attributed to the nanowire growth kinetics and small nanowire diameters, resulting in increased solubility of Sn in Ge at the metastable liquid–solid interface under high pressure. Electrical investigation of the Ge1–xSnx (x = 0.10) nanowires synthesized by the supercritical fluid approach revealed their potential in nanoelectronics and sensor-based applications.

Simultaneous manipulation of multiple boundary conditions in nanoscale heterostructures offers a versatile route to stabilizing unusual structures and emergent phases. Here, we show that a stable supercrystal phase comprising a three-dimensional ordering of nanoscale domains with tailored periodicities can be engineered in PbTiO3–SrRuO3 ferroelectric–metal superlattices. A combination of laboratory and synchrotron X-ray diffraction, piezoresponse force microscopy, scanning transmission electron microscopy and phase-field simulations reveals a complex hierarchical domain structure that forms to minimize the elastic and electrostatic energy. Large local deformations of the ferroelectric lattice are accommodated by periodic lattice modulations of the metallic SrRuO3 layers with curvatures up to 107 m−1. Our results show that multidomain ferroelectric systems can be exploited as versatile templates to induce large curvatures in correlated materials, and present a route for engineering correlated materials with modulated structural and electronic properties that can be controlled using electric fields. Ferroelectric superlattices can present a rich variety of phenomena. Here, in PbTiO3/SrRuO3 superlattices, it is shown that a complex and stable hierarchical supercrystal can form, with the correlated metal of the SrRuO3 layers showing large curvatures.

There has been a relentless pursuit of transverse electric (TE)-dominant deep ultraviolet (UV) optoelectronic devices for efficient surface emitters to replace the environmentally unfriendly mercury lamps. To date, the use of the ternary AlGaN alloy inevitably has led to transverse magnetic (TM)-dominant emission, an approach that is facing a roadblock. Here, we take an entirely different approach of utilizing a binary GaN compound semiconductor in conjunction with ultrathin quantum disks (QDisks) embedded in AlN nanowires (NWs). The growth of GaN QDisks is realized on a scalable and low-cost Si substrate using plasma-assisted molecular beam epitaxy as a highly controllable monolayer growth platform. We estimated an internal quantum efficiency of ∼81% in a wavelength regime of ∼260 nm for these nanostructures. Additionally, strain mapping obtained by high-angle annular dark-field scanning transmission electron microscopy is studied in conjunction with the TE and TM modes of the carrier recombination. Moreover, for the first time, we quantify the TE and TM modes of the PL emitted by GaN QDisks for deep-UV emitters. We observed nearly pure TE-polarized photoluminescence emission at a polarization angle of ∼5°. This work proposes highly quantum-confined ultrathin GaN QDisks as a promising candidate for deep-UV vertical emitters.

Atom probe tomography has been raising in prominence as a microscopy and microanalysis technique to gain sub-nanoscale information from technologically-relevant materials. However, the analysis of some functional ceramics, particularly perovskites, has remained challenging with extremely low yield and success rate. This seems particularly problematic for materials with high piezoelectric activity, which may be difficult to express at the low temperatures necessary for satisfactory atom probe analysis. Here, we demonstrate the analysis of commercial BaTiO3 particles embedded in a metallic matrix. Density-functional theory shows that a metallic coating prevents charge penetration of the electrostatic field, and thereby suppresses the associated volume associated change linked to the piezoelectric effect.

Conducting polymers (CPs) find applications in energy conversion and storage, sensor, and biomedical technologies, once processed into thin films. Hydrophobic CPs, like poly(3,4-ethylenedioxythiophene) (PEDOT), typically require surfactant additives, such as poly(styrenesulfonate) (PSS), to aid their aqueous processability as thin films. However, excess PSS diminishes CP electrochemical performance, biocompatibility, and device stability. Here, we report the electrosynthesis of PEDOT thin films at a polarised liquid|liquid interface, a method non-reliant on conductive solid substrates that produces free-standing, additive-free, biocompatible, easily transferrable, and scalable 2D PEDOT thin films of any shape or size in a single-step at ambient conditions. Electrochemical control of thin film nucleation and growth at the polarised liquid|liquid interface allows control over the morphology, transitioning from 2D (flat on both sides with thickness 850 nm) films. The PEDOT thin films were p-doped (approaching the theoretical limit), showed high π-π conjugation, were processed directly as thin films without insulating PSS, and were thus highly conductive without post-processing. This work demonstrates that interfacial electrosynthesis directly produces PEDOT thin films with distinctive molecular architectures inaccessible in bulk solution or at solid electrode-electrolyte interfaces and emergent properties that facilitate technological advances. In this regard, we demonstrate the PEDOT thin film’s superior biocompatibility as scaffolds for cellular growth, opening immediate applications in organic electrochemical transistor (OECT) devices for monitoring cell behaviour over extended time periods, bio-scaffolds and medical devices, without needing physiologically unstable and poorly biocompatible PSS.

Multiferroic topologies are an emerging solution for future low-power magnetic nanoelectronics due to their combined tuneable functionality and mobility. Here, we show that in addition to being magnetoelectric multiferroic at room temperature, thin-film Aurivillius phase Bi6TixFeyMnzO18 is an ideal material platform for both domain wall and vortex topology-based nanoelectronic devices. Utilizing atomic-resolution electron microscopy, we reveal the presence and structure of 180°-type charged head-to-head and tail-to-tail domain walls passing throughout the thin film. Theoretical calculations confirm the subunit cell cation site preference and charged domain wall energetics for Bi6TixFeyMnzO18. Finally, we show that polar vortex-type topologies also form at out-of-phase boundaries of stacking faults when internal strain and electrostatic energy gradients are altered. This study could pave the way for controlled polar vortex topology formation via strain engineering in other multiferroic thin films. Moreover, these results confirm that the subunit cell topological features play an important role in controlling the charge and spin state of Aurivillius phase films and other multiferroic heterostructures.

Direct colloidal synthesis of multinary metal chalcogenide nanocrystals typically develops dynamically from the binary metal chalcogenide nanocrystals with the subsequent incorporation of additional metal cations from solution during the growth process. Metal seeding of binary and multinary chalcogenides is also established, although the seed is solely a catalyst for nanocrystal nucleation and the metal from the seed has never been exploited as active alloying nuclei. Here we form colloidal Cu–Bi–Zn–S nanorods (NRs) from Bi-seeded Cu2–xS heterostructures. The evolution of these homogeneously alloyed NRs is driven by the dissolution of the Bi-rich seed and recrystallization of the Cu-rich stem into a transitional segment, followed by the incorporation of Zn2+ to form the quaternary Cu–Bi–Zn–S composition. The present study also reveals that the variation of Zn concentration in the NRs modulates the aspect ratio and affects the nature of the majority charge carriers. The NRs exhibit promising thermoelectric properties with very low thermal conductivity values of 0.45 and 0.65 W/mK at 775 and 605 K, respectively, for Zn-poor and Zn-rich NRs. This study highlights the potential of metal seed alloying as a direct growth route to achieving homogeneously alloyed NRs compositions that are not possible by conventional direct methods or by postsynthetic transformations.

The worldwide development of electric vehicles as well as large-scale or grid-scale energy storage to compensate for the intermittent nature of renewable energy generation has led to a surge of interest in battery technology. Understanding the factors controlling battery capacity and, critically, their degradation mechanisms to ensure long-term, sustainable and safe operation requires detailed knowledge of their microstructure and chemistry, and their evolution under operating conditions, on the nanoscale. Atom probe tomography (APT) provides compositional mapping of materials in three dimensions with sub-nanometre resolution, and is poised to play a key role in battery research. However, APT is underpinned by an intense electric field that can drive lithium migration, and many battery materials are reactive oxides, requiring careful handling and sample transfer. Here, we report on the analysis of both anode and cathode materials and show that electric-field driven migration can be suppressed by using shielding by embedding powder particles in a metallic matrix or by using a thin conducting surface layer. We demonstrate that for a typical cathode material, cryogenic specimen preparation and transport under ultra-high vacuum leads to major delithiation of the specimen during the analysis. In contrast, the transport of specimens through air enables the analysis of the material. Finally, we discuss the possible physical underpinnings and discuss ways forward to enable shielding from the electric field, which helps address the challenges inherent to the APT analysis of battery materials.

peer-reviewed The full text of this article will not be available in ULIR until the embargo expires on the 30/01/2021 Flexible electronics has been a field of intense research focus for the diverse and new class of applications not achievable by wafer-based electronics. [1-4] Polymers that are both conductive and stretchable have been put forward as a promising candidate for these device platforms. Due to the often amorphous nature of these material platforms the failure analysis knowledge gained from more traditional devices cannot be applied. The progression and innovation of flexible nanoelectronic manufacturing is dependent on understanding the fundamental physics governing the electronic breakdown of such materials and how to avoid this. In this study we investigate the highly conductive flexible amorphous 2D PEDOT [5-7] layers formed via liquid-liquid interface growth, Figure 1 (a). Utilising aberration corrected TEM and new fast camera technology we study the phase change from amorphous to crystalline at the atomic resolution by in-situ biasing.

peer-reviewed The full text of this article will not be available in ULIR until the embargo expires on the 30/01/2021 Dynamic charged ferroelectric domain walls (CDWs) overturn the classical idea that our electronic circuits need to consist of fixed components of hardware.[1,2] With their own unique electronic properties and exotic functional behaviours all confined to their nanoscale width, DWs represent a completely new 2D material phase.[3-5] The most exciting aspect of CDWs in single crystals is that they can be easily created, destroyed and moved simply by an applied stimulus. The dynamic nature of CDWs gives them the edge over other novel systems and may lead to them being the next promising disruptive quantum technology. This is an area of research at its very early stages with endless possible applications. However, to harness their true potential there is a great deal of the fundamental physics yet to uncover. As the region of interest (CDW) is atomically thin and dynamic, it is essential for the physical characterisation to be at this scale spatially and time-resolved.

Ferroelectric materials, and more specifically ferroelectric domain walls (DWs) have become an area of intense research in recent years. Novel physical phenomena have been discovered at these nanoscale topological polarization discontinuities by mapping out the polarization in each atomic unit cell around the DW in a scanning transmission electron microscope (STEM). However, identifying these features requires an understanding of the polarization in the overall domain structure of the TEM sample, which is often a time-consuming process. Here, a fast method of polarization mapping in the TEM is presented, which can be applied to a range of ferroelectric materials. Due to the coupling of polarization to spontaneous strain, we can isolate different strain states and demonstrate the fast mapping of the domain structure in ferroelectric lead titanate (PTO). The method only requires a high-resolution TEM or STEM image and is less sensitive to zone axis or local strain effects, which may affect other techniques. Thus, it is easily applicable to in-situ experiments. The complimentary benefits of Fourier masking with more advanced mapping strategies and its application to other materials are discussed. These results imply that Fourier masked polarization mapping will be a useful tool for electron microscopists in streamlining their analysis of ferroelectric TEM samples. LAY DESCRIPTION: This paper addresses a problem that often occurs when looking at a ferroelectric material in the Transmission Electron Microscope (TEM). Ferroelectric samples are interesting because they form tiny areas inside themselves with arrow of charge in each one. The thinner the sample, the smaller these regions, called "domains" become. These arrows of charge point in different directions in each domain of the sample. The boundary where these domains meet have interesting properties to study in a TEM but it's important to figure out which way the arrows point in the domains around the boundary. What causes the arrows in the different domains is tiny shifts of different atoms in unit cell away from their neutral position, usually because they're being squeezed by pressure from the domains nearby. The problem is that these tiny atoms moving are difficult to measure and see where the charged arrow is pointing, often it's hard to know how many different domains are even in the sample and where they begin. This paper discusses a method called "Fourier masking" to quickly see what's going on in the overall TEM sample, where the domains are and roughly where the arrows point. It does this by looking at the spacings of the atoms from a magnification where you can just about see the lines of atoms. In lead titanate the unit cell is a rectangle and the arrow always points in line with the long side of the rectangle. The Fourier masking lets you see which direction the long side of the rectangular unit cell is pointing in different parts of your TEM image. The big advantage is that it takes about two minutes to do and uses software that almost every TEM already has. That lets the TEM user quickly know where the domains are in their TEM samples and roughly which way the arrows of charge are pointing. Then they can choose the most interesting features focus on for higher resolution analysis.

Growing III-nitride nanowires on 2D materials is advantageous, as it effectively decouples the underlying growth substrate from the properties of the nanowires. As a relatively new family of 2D materials, MXenes are promising candidates as III-nitride nanowire nucleation layers capable of providing simultaneous transparency and conductivity. In this work, we demonstrate the direct epitaxial growth of GaN nanowires on Ti

Pacific Northwest National Laboratory (PNNL) has leveraged focused ion beam capability at their Category II Nuclear Facility to facilitate nuclear materials analysis and experimentation at the micron scale. For this particular study, micron-size specimens of un-irradiated UO2 fuel pellets of various enrichments were prepared and irradiated to a burnup equivalent of 8–3700 MWd/MTU. This represents first of its kind study of used fuel investigations outside of a hot cell facility, dramatically minimizing resource requirements through reduction in scale. Results of this study provide insight into the initial production of noble metal phase particles in used nuclear fuel at extremely low burnup levels.

Multiferroic topologies are an emerging solution for future low-power magnetic nanoelectronics due to their combined tuneable functionality and mobility. Here, we show that in addition to being magnetoelectric multiferroic at room temperature, thin film Aurivillius phase Bi6TixFeyMnzO18 is an ideal material platform for both domain wall and vortex topology based nanoelectronic devices. Utilising atomic resolution electron microscopy, we reveal the presence and structure of 180˚ type charged head-to-head and tail-to-tail domain walls passing throughout the thin film. Theoretical calculations confirm the sub-unit cell cation site preference and charged domain wall energetics for Bi6TixFeyMnzO18. Finally, we show that polar vortex type topologies also form at out-of-phase boundaries of stacking faults when internal strain and electrostatic energy gradients are altered. This study could pave the way for controlled polar vortex topology formation via strain engineering in other multiferroic thin films. Moreover, these results confirm the sub-unit-cell topological features play an important role in controlling the charge and spin state of Aurivillius phase films and other multiferroic heterostructures.

Multiferroic domain walls are an emerging solution for future low-power nanoelectronics due to their combined tuneable functionality and mobility. Here we show that the magnetoelectric multiferroic Aurivillius phase Bi6TixFeyMnzO18 (B6TFMO) crystal is an ideal platform for domain wall-based nanoelectronic devices. The unit cell of B6TFMO is distinctive as it consists of a multiferroic layer between dielectric layers. We utilise atomic resolution scanning transmission electron microscopy and spectroscopy to map the sub-unit-cell polarisation in B6TFMO thin films. 180˚ charged head-to-head and tail-to-tail domain walls are found to pass through > 8 ferroelectric-dielectric layers of the film. They are structurally similar to BiFeO3 DWs but contain a large surface charge density (σ_s) = 1.09 |e|per perovskite cell, where |e| is elementary charge. Although polarisation is primarily in-plane, c-axis polarisation is identified at head-to-tail domain walls with an associated electromechanical coupling of strain and polarisation. Finally, we reveal that with controlled strain engineering during thin film growth, room-temperature vortexes are formed in the ferroelectric layer. These results confirm that sub-unit-cell topological features can play an important role in controlling the conduction properties and magnetisation state of Aurivillius phase films and other multiferroic heterostructures.

During switching, the microstructure of a ferroelectric normally adapts to align internal dipoles with externally applied electric fields. Dipolar regions (domains), that are favourably oriented, grow at the expense of those in unfavourable orientations and this is manifested in a predictable field-induced motion of the walls that separate one domain from the next. Here, we report the discovery that specific charged 90o domain walls in copper-chlorine boracite move in the opposite direction to that expected, increasing the size of the domain in which polarisation is anti-aligned with the applied electric field. As a consequence, polarisation-field (P-E) hysteresis loops, inferred from optical imaging, show negative gradients and non-transient negative capacitance, throughout the P-E cycle. Switching currents (generated by the relative motion between domain walls and sensing electrodes) confirm this, insofar as their signs are opposite to those expected conventionally. For any given bias, the integrated switching charge due to this anomalous wall motion is found to be directly proportional to time, indicating that the magnitude of the negative capacitance component should be inversely related to frequency (for a given applied ac field). This passes Jonscher’s test for the misinterpretation of positive inductance (associated with an inverse square relationship) and gives confidence that field-induced motion of these specific 90o charged domain walls generates a measurable negative capacitance contribution to the overall dielectric response.

Heavy reliance on extensively studied AlGaN based light emitting diodes (LEDs) to replace environmentally hazardous mercury based ultraviolet (UV) lamps is inevitable. However, external quantum efficiency (EQE) for AlGaN based deep UV emitters remains poor. Dislocation induced nonradiative recombination centers and poor electron-hole wavefunction overlap due to the large polarization field induced quantum confined stark effect (QCSE) in “Al” rich AlGaN are some of the key factors responsible for poor EQE. In addition, the transverse electric polarized light is extremely suppressed in “Al”-rich AlGaN quantum wells (QWs) because of the undesired crossing over among the light hole (LH), heavy hole (HH) and crystal-field split-off (SH) states. Here, optical and structural integrities of dislocation-free ultrathin GaN quantum disk (QDisk) (~ 1.2 nm) embedded in AlN barrier (~ 3 nm) grown employing plasma-assisted molecular beam epitaxy (PAMBE) are investigated considering it as a novel nanostructure to realize highly efficient TE polarized deep UV emitters. The structural and chemical integrities of thus grown QDisks are investigated by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). We, particularly, emphasize the polarization dependent photoluminescence (PL) study of the GaN Disks to accomplish almost purely TE polarized UV (~ 260 nm) light. In addition, we observed significantly high internal quantum efficiency (IQE) of ~ 80 %, which is attributed to the enhanced overlap of the electron-hole wavefunction in extremely quantum confined ultrathin GaN QDisks, thereby presenting GaN QDisks embedded in AlN nanowires as a practical pathway towards the efficient deep UV emitters.

Pulsed laser thermal annealing (LTA) has been thoroughly investigated for the formation of low-resistance stanogermanide contacts on Ge0.91Sn0.09 substrates. Three different metals (Ni, Pt, and Ti) were characterized using a wide laser energy density range (100–500 mJ/cm2). Electrical performance, surface quality, cross-sectional crystallographic, and elemental analysis have been systematically examined in order to identify the ideal process window. Electrical characterization showed that the samples processed by LTA had lower resistance variability compared with the rapid thermal anneal (RTA) counterpart. Among the three metals used, Ni and Pt were the most promising candidates for future sub-nm applications based on the low resistance values. The stanogermanide alloys suffered a high degeneration as the LTA thermal budget increased. Cross-sectional elemental analysis showed a highly unusual Sn segregation effect, particularly for high LTA energy densities, where vertical columns of Sn-rich alloy were formed, also known as cell formation, similar to that seen for Sb hyperdoping of Si when using LTA. This effect is linked to solid solubility and distribution coefficient of Sn in Ge, as well as the velocity of the liquid-solid interface during crystallization as the samples cool.

Multiferroic domain walls are an emerging solution for future low-power nanoelectronics due to their combined tuneable functionality and mobility. Here we show that the magnetoelectric multiferroic Aurivillius phase Bi6TixFeyMnzO18 (B6TFMO) crystal is an ideal platform for domain wall-based nanoelectronic devices. The unit cell of B6TFMO is distinctive as it consists of a multiferroic layer between dielectric layers. We utilise atomic resolution scanning transmission electron microscopy and spectroscopy to map the sub-unit-cell polarisation in B6TFMO thin films. 180˚ charged head-to-head and tail-to-tail domain walls are found to pass through > 8 ferroelectric-dielectric layers of the film. They are structurally similar to BiFeO3 DWs but contain a large surface charge density (σ_s) = 1.09 |e|per perovskite cell, where |e| is elementary charge. Although polarisation is primarily in-plane, c-axis polarisation is identified at head-to-tail domain walls with an associated electromechanical coupling of strain and polarisation. Finally, we reveal that with controlled strain engineering during thin film growth, room-temperature vortexes are formed in the ferroelectric layer. These results confirm that sub-unit-cell topological features can play an important role in controlling the conduction properties and magnetisation state of Aurivillius phase films and other multiferroic heterostructures.

peer-reviewed The full text of this article will not be available in ULIR until the embargo expires on the 30/01/2021 Ferroelectric domain walls (DWs) are the subject of intense research at present in the search for high dielectric, gigahertz responsive materials with novel functionalities[1]. Crucial to the integration of DWs into nanoelectronics is a proper understanding of the local electronic landscape around the wall and the influence this has on the behaviour of the DW under variable electric fields. A high degree of mobility under small electric fields is especially desirable for low power applications which escape from the critical current thresholds required to move magnetic domain walls[2]. Perovskite oxides are prime candidates for tuning the thermodynamic variables affecting the energy landscape of DWs and thus controlling their orientation/charge state[3]. Here we present an investigation into the behaviour of ferroelectric DWs under dynamic fields and the specific charge carriers present at DWs.

A domain wall‐enabled memristor is created, in thin film lithium niobate capacitors, which shows up to twelve orders of magnitude variation in resistance. Such dramatic changes are caused by the injection of strongly inclined conducting ferroelectric domain walls, which provide conduits for current flow between electrodes. Varying the magnitude of the applied electric‐field pulse, used to induce switching, alters the extent to which polarization reversal occurs; this systematically changes the density of the injected conducting domain walls in the ferroelectric layer and hence the resistivity of the capacitor structure as a whole. Hundreds of distinct conductance states can be produced, with current maxima achieved around the coercive voltage, where domain wall density is greatest, and minima associated with the almost fully switched ferroelectric (few domain walls). Significantly, this “domain wall memristor” demonstrates a plasticity effect: when a succession of voltage pulses of constant magnitude is applied, the resistance changes. Resistance plasticity opens the way for the domain wall memristor to be considered for artificial synapse applications in neuromorphic circuits., By changing the density of conducting ferroelectric domain walls that straddle the interelectrode gap, it is shown that a large number of different direct current resistance states can be created, in parallel‐plate thin film lithium niobate capacitors. Surprisingly, such microstructural manipulation can result in colossal changes in device resistance (over twelve orders of magnitude).

We assess the validity of criteria based on size mismatch and thermodynamics in predicting the stability of the rare class of high-entropy alloys (HEAs) that form in the hexagonal close-packed crystal structure. We focus on nanocrystalline HEA particles composed predominantly of Mo, Tc, Ru, Rh, and Pd along with Ag, Cd, and Te, which are produced in uranium dioxide fuel under the extreme conditions of nuclear reactor operation. The constituent elements are fission products that aggregate under the combined effects of irradiation and elevated temperature as high as 1200 °C. We present the recent results on alloy nanoparticle formation in irradiated ceria, which was selected as a surrogate for uranium dioxide, to show that radiation-enhanced diffusion plays an important role in the process. This work sheds light on the initial stages of alloy nanoparticle formation from a uniform dispersion of individual metals. The remarkable chemical durability of such multiple principal element alloys presents a solution, namely, an alloy waste form, to the challenge of immobilizing Tc.

Metallic particles formed in oxide fuels (e.g., UO2) during neutron irradiation have an adverse impact on fuel performance. A fundamental investigation of particle precipitation is needed to predict the fuel performance and potentially improve fuel designs and operations. This study reports on the precipitation of Mo-dominant β-phase particles in polycrystalline CeO2 (surrogate for UO2) films doped with Mo, Pd, Rh, Ru, and Re (surrogate for Tc). In situ heating scanning transmission electron microscopy indicates that particle precipitation starts at ∼1073 K with a limited particle growth to ∼10 nm. While particle concentration increases with increasing temperature, particle size remains largely unchanged up to 1273 K. There is a dramatic change in the microstructure following vacuum annealing at 1373 K, probably due to phase transition of reduced cerium oxide. At the high temperature, particles grow up to 75 nm or larger with distinctive facets. The particles are predominantly composed of Mo with a body-c...

Models for long-term glass alteration are required to satisfy performance predictions of vitrified nuclear waste in various disposal scenarios. Durability parameters are usually extracted from short-term laboratory tests, and sometimes checked with long-term natural experiments on glasses, termed analogues. In this paper, a unique potential ancient glass analogue from Sweden is discussed. The hillfort glass found at Broborg represents a unique case study as a vitrified waste glass analogue to compare to Low Activity Waste glass to be emplaced in near surface conditions at Hanford (USA). Glasses at Broborg have similar and dissimilar compositions to LAW glasses, allowing the testing of long-term alteration of different glass chemistries. In addition, the environmental history of the site is reasonably well documented. Initial investigations on previously collected samples established methodologies for handling and characterizing these artifacts by laboratory methods while preserving their alteration layers and cultural context. Evidence of possible biologically influenced glass alteration, and differential alteration in the 2 types of glass found at the Broborg site is presented.

The combination of strain and electrostatic engineering in epitaxial heterostructures of ferroelectric oxides offers many possibilities for inducing new phases, complex polar topologies, and enhanced electrical properties. However, the dominant effect of substrate clamping can also limit the electromechanical response and often leaves electrostatics to play a secondary role. Releasing the mechanical constraint imposed by the substrate can not only dramatically alter the balance between elastic and electrostatic forces, enabling them to compete on par with each other, but also activate new mechanical degrees of freedom, such as the macroscopic curvature of the heterostructure. In this work, an electrostatically driven transition from a predominantly out-of-plane polarized to an in-plane polarized state is observed when a PbTiO3 /SrTiO3 superlattice with a SrRuO3 bottom electrode is released from its substrate. In turn, this polarization rotation modifies the lattice parameter mismatch between the superlattice and the thin SrRuO3 layer, causing the heterostructure to curl up into microtubes. Through a combination of synchrotron-based scanning X-ray diffraction imaging, Raman scattering, piezoresponse force microscopy and scanning transmission electron microscopy, the crystalline structure and domain patterns of the curved superlattices are investigated, revealing a strong anisotropy in the domain structure and a complex mechanism for strain accommodation. This article is protected by copyright. All rights reserved.

Selective sequestration of sulfate (SO42−) in the form of barite (BaSO4) from alkaline solutions of high ionic strength containing carbonate is problematic due to the preferential formation of BaCO3. Incorporation of sulfate into the insoluble and thermally stable BaSO4 phase can potentially benefit radioactive waste processing by reducing operational challenges and suppressing volatilization of other waste components such as technetium-99. To enhance selectivity of SO42− sequestration, a series of Ba–Sn nanocomposite materials was prepared using simple hydrothermal synthesis from different Sn(II) and Sn(IV) precursors. Structural characterization indicated that all obtained products predominantly contained BaSn(OH)6 and Ba2SnO2(OH)4·10H2O nanocrystalline phases which were disrupted upon exposure to SO42− due to formation of BaSO4. Performance of the Ba–Sn materials was tested using complex alkaline solutions simulating radioactive waste containing 0.094 M SO42− and 0.5 M CO32− among other constituents. About 54–66% of SO42− was converted to BaSO4 when a quantity of Ba–Sn material containing approximately a stoichiometric amount of Ba2+ relative to SO42− was used. In comparison, previous studies indicate negligible BaSO4 formation under similar conditions when a simple Ba2+ salt is used. This improvement is attributed to the selective replacement of the stannate by SO42−. Thermal stability of the sulfate-loaded product material up to 1100 °C was demonstrated. The obtained materials promise a convenient and economical option for the selective sequestration or removal of SO42− from complex carbonate containing solutions.

A better understanding of how production pathway affects the final product is required in order to produce targeted syntheses, but many of the classical ex situ techniques used for studying nanoparticle growth are unsuitable as stand-alone methods for identifying and characterizing growth mechanisms. Using a combination of high resolution transmission electron microscopy (TEM), cryogenic TEM, liquid cell scanning electron microscopy, and optical microscopy we monitor europium oxalate growth over the range of nanometers to tens of micrometers and identify potential crystal growth pathways. Interpretation of the evolving crystallites reveals the significant impact of inhomogeneity in diffusion fields on diffusion limited crystal growth. We also compare the effects of stirring during crystal growth as an example of how changing processing conditions changes growth mechanisms.

Epsilon-phase alloy precipitates have been observed with varied compositions and sizes in spent nuclear fuels, such as UO2. The presence of the inclusions, along with other oxide precipitates, gas bubbles, and irradiation-induced structural defects, can significantly degrade the physical properties of the fuel. To predict fuel performance, a fundamental study of the precipitation processes is needed. This study uses ceria (CeO2) as a surrogate for UO2. Polycrystalline CeO2 films doped with Mo, Ru, Rh, Pd, and Re (surrogate for Tc) were grown at 823 K using pulsed laser deposition, irradiated at 673 K with He+ ions, and subsequently annealed at higher temperatures. A number of methods, including transmission electron microscopy and atom probe tomography, were applied to characterize the samples. The results indicate that there is a uniform distribution of the doped metals in the as-grown CeO2 film. Pd particles of ∼3 nm in size appear near the dislocation edges after He+ ion irradiation to ∼13 dpa. Thermal...

The behaviour of palladium and nickel deposited on mechanically exfoliated samples of 2D transition metal dichalcogenides (MoS2 , WS2 and WSe2 ) via e-beam evaporation was investigated. Sputtering of metals on the 2D flakes allowed for interaction of the metal and TMD to be investigated on the A scale in an aberration-corrected transmission electron microscope. Through low energy sputtering, metals can be deposited on 2D materials without causing damage to the thin flakes. The material's interaction is investigated on the atomic scale via high resolution scanning transmission electron microscopy in high angle annular dark-field imaging. Initially, the effect of thermal annealing on the stability of the Pd-2D interaction was investigated, revealing the remarkable difference in particle stability between the 2D materials. Nickel deposition however only resulted in oxidised amorphous particles. The oxide particles' cross-sectional area and circularity were independent of the TMD substrate thickness, type, or deposition rate. LAY DESCRIPTION: Understanding the interaction between metals and 2D materials is imperative for future device functionalisation. Palladium and nickel were deposited on samples of 2D transition metal dichalcogenides (MoS2 , WS2 and WSe2 ) via e-beam evaporation. Low energy introduced metal to the 2D materials without causing damage to the thin flakes. The metal-2D interaction was investigated on the A scale via high resolution scanning transmission electron microscopy in high angle annular dark-field imaging. The interaction between the Pd and the 2Ds was investigated to see whether Pd is a viable contact solution for TMD materials and to study the metal-2D interaction at the atomic level. Effect of annealing and heat on the stability of the Pd-2D interaction was investigated, showing Pd-WSe2 to have high particle stability up to 200 °C. In contrast, the Pd-MoS2 and Pd-WS2 had lower particle stability when heated, revealing particle agglomeration and changes. Nickel was found to oxidise into amorphous oxide particles quickly after deposition. The oxide particles' characteristics were independent of the TMD substrate thickness andtype, and independent of the rate at which metal was deposited.

The combination of two active Li-ion materials (Ge and Sn) can result in improved conduction paths and higher capacity retention. Here we report; for the first time; the implementation of Ge1-xSnx alloy nanowires as anode materials for Li-ion batteries. Ge1-xSnx alloy nanowires have been successfully grown via vapor-liquid-solid (VLS) technique directly on stainless steel current collectors. Ge1-xSnx (x = 0.048) nanowires were predominantly seeded from the Au0.80Ag0.20 catalysts with negligible amount of growth was also directly catalysed from stainless steel substrate. The electrochemical performance of the the Ge1-xSnx nanowires as an anode material for Li-ion batteries was investigated via galvanostatic cycling and detailed analysis of differential capacity plots. The nanowire electrodes demonstrated an exceptional capacity retention of 93.4 % from the 2nd to the 100th charge at a C/5 rate, while maintaining a specific capacity value of ~921 mAh/g after 100 cycles. Voltage profiles and differential capacity plots revealed that the Ge1-xSnx nanowires behave as an alloying mode anode material, as reduction/oxidation peaks for both Ge and Sn were observed, however it is clear that the reversible lithiation of Ge is responsible for the majority of the charge stored.

peer-reviewed Although the existence of a five-metal (Mo-Tc-Ru-Rh-Pd) phase – as nanoparticles observed in irradiated nuclear fuel – has been known for more than half a century, the chemical and physical mechanisms controlling the formation and behavior of such particles remain stubbornly elusive. We present in this work new evidence for the presence of a separate nonmetallic phase associated with the metallic particles and containing a significant fraction of Te in addition to Pd. While this new phase potentially complicates the thermodynamic picture of a mixed alloy in equilibrium with the surrounding fuel environment, it also provides new clues in the search for a chemical mechanism for Pd migration through the uranium dioxide matrix and the nucleation behavior of the particles. Fractionation between phases may subsequently affect the mechanical performance of fuels during irradiation and their interactions with the surrounding environment during long-term waste storage.

We have made observations of noble metal phase fission-product agglomerates and gaseous xenon within the fuel-cladding interaction (FCI) zone of a high-burnup UO2 fuel. The FCI is the boundary between the UO2 pellet outer surface and the inner wall of the oxidized Zr-liner/cladding of the fuel rod. These fission-product agglomerates are well known to occur within the spent fuel matrix, and although radionuclides have been reported by others, we reveal aspects of their speciation and morphology. That they occur as discrete particles in the oxidized Zr liner, suggests the occurrence of hitherto unknown processes in the FCI zone during reactor operation, and this may have implications for the long-term storage and disposal of these types of materials. As expected, the particle agglomerates, which ranged in size from the nanometer scale to the micrometer scale, contained mainly Mo, Ru, Tc, Rh, and Pd; however, we also found significant quantities of Te associated with Pd. Indeed, we found nanometer scale separation of the distinct Pd/Te phase from the other fission products within the particles. Often associated with the particles was concentrations of uranium, sometimes appearing as a “cloud” with a tail emanating from the fuel into the oxidized cladding liner. Many of the noble metal phase particles appeared as fractured clusters separated by Xe-gas-filled voids. Possible mechanisms of formation or transport in the cladding liner are presented.

Simultaneous manipulation of multiple boundary conditions in nanoscale heterostructures offers a versatile route to stabilizing unusual structures and emergent phases. Here, we show that a stable supercrystal phase comprising a three-dimensional ordering of nanoscale domains with tailored periodicities can be engineered in PbTiO

Domain wall nanoelectronics is a rapidly evolving field, which explores the diverse electronic properties of the ferroelectric domain walls for application in low-dimensional electronic systems. One of the most prominent features of the ferroelectric domain walls is their electrical conductivity. Here, using a combination of scanning probe and scanning transmission electron microscopy, the mechanism of the tunable conducting behavior of the domain walls in the sub-micrometer thick films of the technologically important ferroelectric LiNbO