Zinc Oxide Nanostructure Deposition into Sub-5 nm Vertical Mesopores in Silica Hard Templates by Atomic Layer Deposition.

Nanostructures synthesised by hard-templating assisted methods are advantageous as they retain the size and morphology of the host templates which are vital characteristics for their intended applications. A number of techniques have been employed to deposit materials inside porous templates, such as electrodeposition, vapour deposition, lithography, melt and solution filling, but most of these efforts have been applied with pore sizes higher in the mesoporous regime or even larger. Here, we explore atomic layer deposition (ALD) as a method for nanostructure deposition into mesoporous hard templates consisting of mesoporous silica films with sub-5 nm pore diameters. The zinc oxide deposited into the films was characterised by small-angle X-ray scattering, X-ray diffraction and energy-dispersive X-ray analysis.

Experimental and theoretical evidence for unprecedented strong interactions of gold atoms with boron on boron/sulfur-doped carbon surfaces.

The 16e square-planar bis-thiolato-Au(iii) complexes [AuIII(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)2][NBu4] (Au-1) and [AuIII(4-methyl-1,2-benzenedithiolato)2][NBu4] (Au-2) have been synthesized and fully characterized. Au-1 and Au-2 were encapsulated in the symmetrical triblock copolymer poloxamer (Pluronic®) P123 containing blocks of poly(ethylene oxide) and poly(propylene oxide), giving micelles AuMs-1 and AuMs-2. High electron flux in scanning transmission electron microscopy (STEM) was used to generate single gold atoms and gold nanocrystals on B/S-doped graphitic surfaces, or S-doped amorphous carbon surfaces from AuMs-1 and AuMs-2, respectively. Electron energy loss spectroscopy (EELS) data suggested strong interactions of gold atoms/nanocrystals with boron in the B/S-doped graphitic matrix. Density-functional theory (DFT) calculations, also supported the experimental findings, pointing towards strong Au-B bonds, depending on the charge on the Au-(B-graphene) fragment and the presence of further defects in the graphene lattice.

Film before aggregates: an operando GISAXS study on electrochemically assisted surfactant assembly.

The process of electrochemically assisted surfactant assembly was followed in real time by grazing incidence small angle X-ray scattering with the aim to deconvolute the formation of mesoporous silica film and unwanted porous particles. The X-ray technique proved to be useful for the characterisation of this process, as it takes place at a very dynamic, solid/liquid interface. This paper shows the electrochemically driven onset and evolution of silica/surfactant structures. Additional control experiments indicate the formation of vertically aligned structures without the use of an electric field, although it seems to be beneficial for increased pore ordering.

Modelling fine-sliced three dimensional electron diffraction data with dynamical Bloch-wave simulations.

Recent interest in structure solution and refinement using electron diffraction (ED) has been fuelled by its inherent advantages when applied to crystals of sub-micrometre size, as well as its better sensitivity to light elements. Currently, data are often processed with software written for X-ray diffraction, using the kinematic theory of diffraction to generate model intensities - despite the inherent differences in diffraction processes in ED. Here, dynamical Bloch-wave simulations are used to model continuous-rotation electron diffraction data, collected with a fine angular resolution (crystal orientations of ∼0.1°). This fine-sliced data allows a re-examination of the corrections applied to ED data. A new method is proposed for optimizing crystal orientation, and the angular range of the incident beam and the varying slew rate are taken into account. Observed integrated intensities are extracted and accurate comparisons are performed with simulations using rocking curves for a (110) lamella of silicon 185 nm thick. R1 is reduced from 26% with the kinematic model to 6.8% using dynamical simulations.

Mesoporous silica films as hard templates for electrodeposition of nanostructured gold.

Metallic nanostructures have widespread applications in fields including materials science, electronics and catalysis. Mesoporous silica films synthesised by evaporation induced self-assembly and electrochemically assisted self-assembly with pores below 10 nm were used as hard templates for the electrodeposition of Au nanostructures. Electrodeposition conditions were optimised based on pore orientation and size. The growth of nanostructures was initiated at the electrode surface as confirmed by microscopy. The hard templates and Au electrodeposits were characterised electrochemically as well as with X-ray diffraction, small angle scattering and transmission electron microscopy. Finally, mesoporous silica hard templates were removed by hydrofluoric acid etching and stable Au nanoparticles on different electrode surfaces were achieved.

3D-structured mesoporous silica memristors for neuromorphic switching and reservoir computing.

Memristors are emerging as promising candidates for practical application in reservoir computing systems that are capable of temporal information processing. Here, we experimentally implement a physical reservoir computing system using resistive memristors based on three-dimensional (3D)-structured mesoporous silica (mSiO2) thin films fabricated by a low cost, fast and vacuum-free sol-gel technique. The in situ learning capability and a classification accuracy of 100% on a standard machine learning dataset are experimentally demonstrated. The volatile (temporal) resistive switching in diffusive memristors arises from the formation and subsequent spontaneous rupture of conductive filaments via diffusion of Ag species within the 3D-structured nanopores of the mSiO2 thin film. Besides volatile switching, the devices also exhibit a bipolar non-volatile resistive switching behavior when the devices are operated at a higher compliance current level. The implementation of mSiO2 thin films opens the route to fabricate a simple and low cost dynamic memristor with a temporal information process functionality, which is essential for neuromorphic computing applications.

Electron Beam Transparent Boron Doped Diamond Electrodes for Combined Electrochemistry-Transmission Electron Microscopy.

The majority of carbon based transmission electron microscopy (TEM) platforms (grids) have a significant sp2 carbon component. Here, we report a top down fabrication technique for producing freestanding, robust, electron beam transparent and conductive sp3 carbon substrates from boron doped diamond (BDD) using an ion milling/polishing process. X-ray photoelectron spectroscopy and electrochemical measurements reveal the sp3 carbon character and advantageous electrochemical properties of a BDD electrode are retained during the milling process. TEM diffraction studies show a dominant (110) crystallographic orientation. Compared with conventional carbon TEM films on metal supports, the BDD-TEM electrodes offer superior thermal, mechanical and electrochemical stability properties. For the latter, no carbon loss is observed over a wide electrochemical potential range (up to 1.80 V vs RHE) under prolonged testing times (5 h) in acid (comparable with accelerated stress testing protocols). This result also highlights the use of BDD as a corrosion free electrocatalyst TEM support for fundamental studies, and in practical energy conversion applications. High magnification TEM imaging demonstrates resolution of isolated, single atoms on the BDD-TEM electrode during electrodeposition, due to the low background electron scattering of the BDD surface. Given the high thermal conductivity and stability of the BDD-TEM electrodes, in situ monitoring of thermally induced morphological changes is also possible, shown here for the thermally induced crystallization of amorphous electrodeposited manganese oxide to the electrochemically active γ-phase.

Confining the growth of mesoporous silica films into nanospaces: towards surface nanopatterning.

The combination of lithographic methods and sol gel bottom-up techniques is a promising approach for nanopatterning substrates. The integration and scalable fabrication of such substrates are of great interest for the development of nanowire-based materials opening potentialities in new technologies. We demonstrate the deposition of ordered mesoporous silica into nanopatterned silica substrates by dip coating. Using scanning electron microscopy and grazing incidence small angle X-ray scattering, the effect of the sol composition on the pore ordering was probed. Optimising the sol composition using anodic alumina membranes as confined spaces, we showed how the pH controlled the transformation from circular to columnar mesophase. Vertical mesopores were obtained with very good repeatability. The effect of the sol chemistry on the surfactant curvature was then shown to be similar in nanopatterned substrates made by e-beam lithography.

AC-assisted deposition of aggregate free silica films with vertical pore structure.

Silica thin films with vertical nanopores are useful to control access to electrode surfaces and may act as templates for growth of nanomaterials. The most effective method to produce these films, electrochemically assisted surfactant assembly, also produces aggregates of silica particles. This paper shows that growth with an AC signal superimposed onto the potential avoids the aggregates and only very small numbers of single particles are found. This finding is linked to better control of the diffusion field of hydroxide ions that are responsible for particle growth. The resultant films are smooth, with very well-ordered hexagonal pore structures.

Ferroelectric incommensurate spin crystals.

Ferroics, especially ferromagnets, can form complex topological spin structures such as vortices1 and skyrmions2,3 when subjected to particular electrical and mechanical boundary conditions. Simple vortex-like, electric-dipole-based topological structures have been observed in dedicated ferroelectric systems, especially ferroelectric-insulator superlattices such as PbTiO3/SrTiO3, which was later shown to be a model system owing to its high depolarizing field4-8. To date, the electric dipole equivalent of ordered magnetic spin lattices driven by the Dzyaloshinskii-Moriya interaction (DMi)9,10 has not been experimentally observed. Here we examine a domain structure in a single PbTiO3 epitaxial layer sandwiched between SrRuO3 electrodes. We observe periodic clockwise and anticlockwise ferroelectric vortices that are modulated by a second ordering along their toroidal core. The resulting topology, supported by calculations, is a labyrinth-like pattern with two orthogonal periodic modulations that form an incommensurate polar crystal that provides a ferroelectric analogue to the recently discovered incommensurate spin crystals in ferromagnetic materials11-13. These findings further blur the border between emergent ferromagnetic and ferroelectric topologies, clearing the way for experimental realization of further electric counterparts of magnetic DMi-driven phases.

Large-Area Electrodeposition of Few-Layer MoS2 on Graphene for 2D Material Heterostructures.

Heterostructures involving two-dimensional (2D) transition metal dichalcogenides and other materials such as graphene have a strong potential to be the fundamental building block of many electronic and optoelectronic applications. The integration and scalable fabrication of such heterostructures are of the essence in unleashing the potential of these materials in new technologies. For the first time, we demonstrate the growth of few-layer MoS2 films on graphene via nonaqueous electrodeposition. Through methods such as scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, energy- and wavelength-dispersive X-ray spectroscopies, and X-ray photoelectron spectroscopy, we show that this deposition method can produce large-area MoS2 films with high quality and uniformity over graphene. We reveal the potential of these heterostructures by measuring the photoinduced current through the film. These results pave the way toward developing the electrodeposition method for the large-scale growth of heterostructures consisting of varying 2D materials for many applications.

Controlling palladium morphology in electrodeposition from nanoparticles to dendrites via the use of mixed solvents.

By changing the mole fraction of water (χwater) in the solvent acetonitrile (MeCN), we report a simple procedure to control nanostructure morphology during electrodeposition. We focus on the electrodeposition of palladium (Pd) on electron beam transparent boron-doped diamond (BDD) electrodes. Three solutions are employed, MeCN rich (90% v/v MeCN, χwater = 0.246), equal volumes (50% v/v MeCN, χwater = 0.743) and water rich (10% v/v MeCN, χwater = 0.963), with electrodeposition carried out under a constant, and high overpotential (-1.0 V), for fixed time periods (50, 150 and 300 s). Scanning transmission electron microscopy (STEM) reveals that in MeCN rich solution, Pd atoms, amorphous atom clusters and (majority) nanoparticles (NPs) result. As water content is increased, NPs are again evident but also elongated and defected nanostructures which grow in prominence with time. In the water rich environment, NPs and branched, concave and star-like Pd nanostructures are now seen, which with time translate to aggregated porous structures and ultimately dendrites. We attribute these observations to the role MeCN adsorption on Pd surfaces plays in retarding metal nucleation and growth.

Atomic level termination for passivation and functionalisation of silicon surfaces.

Chemical treatments play an essential role in the formation of high quality interfaces between materials, including in semiconductor devices, and in the functionalisation of surfaces. We have investigated the effects of hydrogen and fluorine termination of (100)-orientation silicon surfaces over a range of length scales. At the centimetre scale, lifetime measurements show clean silicon surfaces can be temporarily passivated by a short treatment in both HF(2%) : HCl(2%) and HF(50%) solutions. The lifetime, and hence surface passivation, becomes better with immersion time in the former, and worse with immersion time in the latter. At the nanometre scale, X-ray photoelectron spectroscopy and atomic force microscopy show treatment with strong HF solutions results in a roughened fluorine-terminated surface. Subsequent superacid-derived surface passivation on different chemically treated surfaces shows considerably better passivation on surfaces treated with HF(2%) : HCl(2%) compared to HF. Lifetime data are modelled to understand the termination in terms of chemical and field effect passivation at the centimetre scale. Surfaces passivated with Al2O3 grown by atomic layer deposition behave similarly when either HF(2%) : HCl(2%) or HF(50%) are used as a pre-treatment, possibly because of the thin silicon dioxide interlayer which subsequently forms. Our study highlights that chemical pre-treatments can be extremely important in the creation of high quality functionalised surfaces.

Partial Scanning Transmission Electron Microscopy with Deep Learning.

Compressed sensing algorithms are used to decrease electron microscope scan time and electron beam exposure with minimal information loss. Following successful applications of deep learning to compressed sensing, we have developed a two-stage multiscale generative adversarial neural network to complete realistic 512 × 512 scanning transmission electron micrographs from spiral, jittered gridlike, and other partial scans. For spiral scans and mean squared error based pre-training, this enables electron beam coverage to be decreased by 17.9× with a 3.8% test set root mean squared intensity error, and by 87.0× with a 6.2% error. Our generator networks are trained on partial scans created from a new dataset of 16227 scanning transmission electron micrographs. High performance is achieved with adaptive learning rate clipping of loss spikes and an auxiliary trainer network. Our source code, new dataset, and pre-trained models are publicly available.

Polarization Screening Mechanisms at La0.7Sr0.3MnO3-PbTiO3 Interfaces.

The structural, electronic, and magnetic properties of interfaces between epitaxial La0.7Sr0.3MnO3 and PbTiO3 have been explored via atomic resolution transmission electron microscopy of a functional multiferroic tunnel junction. Measurements of the polar displacements and octahedral tilting show the competition between the two distortions at the interface and demonstrate strong dependence on the polarization orientation. The density functional theory provides information on the electronic and magnetic properties, where the interface termination plays a crucial role in the screening mechanisms.

Defect Dynamics in Self-Catalyzed III-V Semiconductor Nanowires.

The droplet consumption step in self-catalyzed III-V semiconductor nanowires can produce material that contains a high density of line defects. Interestingly, these defects are often associated with twin boundaries and have null Burgers vector, i.e., no long-range strain field. Here, we analyze their stability by considering the forces that act on them and use in situ aberration corrected scanning transmission electron microscopy (STEM) to observe their behavior in GaAsP nanowires (NWs) using short annealing cycles. Their movement appears to be consistent with the thermally activated single- or double-kink mechanisms of dislocation glide, with velocities that do not exceed 1 nm s-1. We find that motion of individual defects depends on their size, position, and surrounding environment and set an upper limit to activation energy around 2 eV. The majority of defects (>70%) are removed by our postgrowth annealing for several seconds at temperatures in excess of 640 °C, suggesting that in situ annealing during growth at lower temperatures would significantly improve material quality. The remaining defects do not move at all and are thermodynamically stable in the nanowire.

Self-Formed Quantum Wires and Dots in GaAsP-GaAsP Core-Shell Nanowires.

Quantum structures designed using nanowires as a basis are excellent candidates to achieve novel design architectures. Here, triplets of quantum wires (QWRs) that form at the core-shell interface of GaAsP-GaAsP nanowires are reported. Their formation, on only three of the six vertices of the hexagonal nanowire, is governed by the three-fold symmetry of the cubic crystal on the (111) plane. In twinned nanowires, the QWRs are segmented, to alternating vertices, forming quantum dots (QDs). Simulations confirm the possibility of QWR and QD-like behavior from the respective regions. Optical measurements confirm the presence of two different types of quantum emitters in the twinned individual nanowires. The possibility to control the relative formation of QWRs or QDs, and resulting emission wavelengths of the QDs, by controlling the twinning of the nanowire core, opens up new possibilities for designing nanowire devices.

Improving electron micrograph signal-to-noise with an atrous convolutional encoder-decoder.

We present an atrous convolutional encoder-decoder trained to denoise electron micrographs. It consists of a modified Xception backbone, atrous convoltional spatial pyramid pooling module and a multi-stage decoder. Our neural network was trained end-to-end using 512  ×  512 micrographs created from a large dataset of high-dose ( > 2500 counts per pixel) micrographs with added Poisson noise to emulate low-dose ( ≪  300 counts per pixel) data. It was then fine-tuned for high dose data (200-2500 counts per pixel). Its performance is benchmarked against bilateral, Gaussian, median, total variation, wavelet, and Wiener restoration methods with their default parameters. Our network outperforms their best mean squared error and structural similarity index performances by 24.6% and 9.6% for low doses and by 43.7% and 5.5% for high doses. In both cases, our network's mean squared error has the lowest variance. Source code and links to our high-quality dataset and pre-trained models are available at https://github.com/Jeffrey-Ede/Electron-Micrograph-Denoiser.

Towards a 3D GeSbTe phase change memory with integrated selector by non-aqueous electrodeposition.

We have recently reported a new method for the electrodeposition of thin film and nanostructured phase change memory (PCM) devices from a single, highly tuneable, non-aqueous electrolyte. The quality of the material was confirmed by phase cycling via electrical pulsed switching of both 100 nm nano-cells and thin film devices. This method potentially allows deposition into extremely small confined cells down to less than 5 nm, 3D lay-outs that require non-line-of-sight techniques, and seamless integration of selector devices. As electrodeposition requires a conducting substrate, the key condition for electronic applications based on this method is the use of patterned metal lines as the working electrode during the electrodeposition process. In this paper, we show the design and fabrication of a 2D passive memory matrix in which the word lines act as the working electrode and nucleation site for the growth of confined cells of Ge-Sb-Te. We will discuss the precursor requirement for deposition from non-aqueous, weakly coordinating solvents, show the transmission electron microscopy analysis of the electrodeposition growth process and elemental distribution in the deposits, and show the fabrication and characterisation of the Ge-Sb-Te memory matrix.

Quantitative High-Dynamic-Range Electron Diffraction of Polar Nanodomains in Pb2 ScTaO6.

Highly B-site ordered Pb2 ScTaO6 crystals are studied as a function of temperature via dielectric spectroscopy and in situ high-dynamic-range electron diffraction. The degree of ordering is examined on the local and macroscopic scale and is determined to be 76%. Novel analysis of the electron diffraction patterns provides structural information with two types of antiferroelectric displacements determined to be present in the polar structure. It is then found that a low-temperature transition occurs on cooling at ≈210 K that is not present on heating. This phenomenon is discussed in terms of the freezing of dynamic polar nanodomains where a high density of domain walls creates a metastable state.