Search

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

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

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.

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.

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

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.

Charged domain walls (DWs) in ferroelectric materials are an area of intense research. Microscale strain has been identified as a method of inducing arrays of twin walls to meet at right angles, forming needlepoint domains which exhibit novel material properties. Atomic scale characterisation of the features exhibiting these exciting behaviours was inaccessible with the piezoresponse force microscopy resolution of previous work. Here we use aberration corrected scanning transmission electron microscopy to observe short, stepped, highly charged DWs at the tip of the needle points in ferroelectric PbTiO3. Reverse Ti4+ shift polarisation mapping confirms the head-to-head polarisation in adjacent domains. Strain mapping reveals large deviations from the bulk and a wider DW with a high Pb2+ vacancy concentration. The extra screening charge is found to stabilise the DW perpendicular to the opposing polarisation vectors and thus constitutes the most highly charged DW possible in PbTiO3. This feature at the needle point junction is a 5 nm × 2 nm channel running through the sample and is likely to have useful conducting properties. We envisage that similar junctions can be formed in other ferroelastic materials and yield exciting phenomena for future research. Domain walls are the basic building blocks of a ferroic system and determine the overall ferroic properties. Here, the authors use aberration corrected scanning transmission electron microscopy to observe the formation of charged needle point domain walls in ferroelectric PbTiO3 and how their characteristics depend on the lead vacancy concentration.

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).

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.

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

Ferroelectric domain wall (DW) based nano-electronics is an emerging new field of research. It is only recently with advancements in electron and atomic force microscopy instrumentation that the complex nature of these 2D entities can be probed. In this Research Update, the advances in aberration corrected scanning transmission electron microscopy applied to ferroelectric topological defects are summarized. We discuss sub-atomic imaging and diffraction techniques used to observe changes in polarization, chemical composition, charge density, and strain at DWs and vortices. We further highlight the current achievements in mapping the 3D nature of ferroelectric polar skyrmions and in situ biasing. This Review will focus on both the fundamental physics of DW and polar vortex formation and their dynamics. Finally, we discuss how electron spectroscopy can be used to relate the quantified structural distortions of polar topological entities to changes in their oxidation state and band structure.

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 LiNbO3 is explored. It is found that the electric bias generates stable domains with strongly inclined domain boundaries with the inclination angle reaching 20° with respect to the polar axis. The head-to-head domain boundaries exhibit high conductance, which can be modulated by application of the sub-coercive voltage. Electron microscopy visualization of the electrically written domains and piezoresponse force microscopy imaging of the very same domains reveals that the gradual and reversible transition between the conducting and insulating states of the domain walls results from the electrically induced wall bending near the sample surface. The observed modulation of the wall conductance is corroborated by the phase-field modeling. The results open a possibility for exploiting the conducting domain walls as the electrically controllable functional elements in the multilevel logic nanoelectronics devices.