Extreme Dewetting Resistance and Improved Visible Transmission of Ag Layers Using Sub-Nanometer Ti Capping Layers.

As technology development drives the thickness of thin film depositions down into the nano regime, understanding and controlling the dewetting of thin films has become essential for many applications. The dewetting of ultra-thin Ag (9 nm) films with Ti (0.5 nm) adhesion and capping layers on glass substrates was investigated in this work. Various thin film stacks were created using magnetron sputtering and were analyzed using scanning electron microscopy/energy dispersive X-rays, Vis/IR spectrometry, and four four-point probe resistivity measurements. Upon annealing for 5 h in air at 250 °C, the addition of a 0.5 nm thick Ti capping layer reduced the dewet area by an order of magnitude. This is reflected in film resistivity, which remained 2 orders of magnitude lower than uncapped variants. This Ti/Ag/Ti structure was then deployed in a typical low-emissivity window coating structure with additional antireflective layers of AZO, resulting in a superior performance upon annealing. These results demonstrate an easy, manufacturable process that improves the longevity of devices and products containing thin Ag films.

Monolayer Capping Provides Close to Optimal Resistance to Laser Dewetting of Au Films.

Next-generation heat-assisted magnetic recording (HAMR) relies on fast, localized heating of the magnetic medium during the write process. Au plasmonic near-field transducers are an attractive solution to this challenge, but increased thermal stability of Au films is required to improve long-term reliability. This work compares the effect of nanoscale Al, AlOx, and Ta capping films on Au thin films with Ti or Ta adhesion layers for use in HAMR and other high-temperature plasmonic applications. Thermal stability is investigated using a bespoke laser dewetting system, and SEM and AFM are extensively used to interrogate the resulting dewet areas. The most effective capping layers are found to be 0.5-1 nm of Al or AlOx, which can eliminate dewetting under certain conditions. Even one monolayer of AlOx is shown to be highly effective in reducing dewetting. In the case of thicker capping layers of Ta and AlOx, the Au film can easily dewet underneath, leaving an intact capping layer. It is concluded that thinner capping layers are most effective against dewetting as the Au cannot dewet without breaking them and pulling them apart during the dewetting process. A simple model based on energetics considerations is developed, which explains how thinner capping layers can more effectively protect the metal from pore or fissure creation. The model provides some convenient guidelines for choosing both the substrate and capping layer, for a given metal, to maximize the resistance to laser-induced damage.

A Retrofittable Photoelectron Gun for Low-Voltage Imaging Applications in the Scanning Electron Microscope.

Low-voltage scanning electron microscopy is a powerful tool for examining surface features and imaging beam-sensitive materials. Improving resolution during low-voltage imaging is then an important area of development. Decreasing the effect of chromatic aberration is one solution to improving the resolution and can be achieved by reducing the energy spread of the electron source. Our approach involves retrofitting a light source onto a thermionic lanthanum hexaboride (LaB6) electron gun as a cost-effective low energy-spread photoelectron emitter. The energy spread of the emitter's photoelectrons is theorized to be between 0.11 and 0.38 eV, depending on the photon energy of the ultraviolet (UV) light source. Proof-of-principle images have been recorded using this retrofitted photoelectron gun, and an analysis of its performance is presented.

Templated Synthesis of SiO2 Nanotubes for Lithium-Ion Battery Applications: An In Situ (Scanning) Transmission Electron Microscopy Study.

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core-shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge-discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li+-ion batteries.

Nanoscale mapping of shifts in dark plasmon modes in sub 10 nm aluminum nanoantennas.

In this work, we report the fabrication and spectroscopic characterization of subwavelength aluminum nanocavities-consisting of hexamer or tetramer clusters of sub 10 nm width Al nanorods-with tunable localized surface plasmon resonance (LSPR) energies on suspended SiNxmembranes. Here the volume plasmon (VP) and LSPR modes of lithographically-fabricated Al nanocavities are revealed by low-loss electron energy-loss spectroscopy (EELS) in an aberration corrected scanning transmission electron microscope (STEM). We show that the existence of grain boundaries (GBs) in these nanocavities results in shifts in the VP energy and a reduction in the VP lifetime. We map the VP energy and lifetime across GBs and we observe a decrease in VP energy and lifetime at GBs that is consistent with a reduction in free carrier density and increased plasmon scattering at these locations. Dipolar LSPR modes resonant in the UV and blue regions of the electromagnetic spectrum as well as higher-energy optically dark quadrupolar and hexapolar LSPR modes are also observed and mapped by STEM and EELS. All LSPR modes are confirmed via electromagnetic simulations based on the boundary element method. Both tetramer and hexamer structures support the excitation of dipolar bright and dipolar dark modes. Finally, we find that asymmetries in fabricated nanorod hexamer and tetramer nanocavities result in a mode mixing leading to a shift in dipolar dark LSPR modes.

Charged Domain Wall and Polar Vortex Topologies in a Room-Temperature Magnetoelectric Multiferroic Thin Film.

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.

Inhibition of vacuum sublimation artefacts for (Scanning) Transmission Electron Microscopy ((S)TEM) of sulphur samples via encapsulation.

Lithium-sulfur battery is one of promising candidates for next-generation energy storage device due to the sulfur cathode material with low cost and nontoxicity, and super high theoretical energy density (nearly 2600Wh kg -1) and specific energy (2567Wh kg -1). Sulphur, however, poses a few interesting challenges before it can gain widespread utilisation. The biggest issue is known as the polysulphide shuttling effect which contributes to rapid capacity loss after cycling. Accurate characterisation of sulphur cathodic materials becomes critical to our understanding polysulphide shuttling effect in the quest of finding mitigating solutions. Electron microscopy is playing a crucial role in battery research in determining structure-property-function relations. However, sulphur undergoes sublimation at a point above the typical pressures found in the column of a transmission electron microscope (TEM) at room temperature. This makes the imaging and characterisation of any sort of nanostructured sulphur samples challenging, as the material will be modified or even disappear rapidly as soon as it is inserted into the TEM vacuum. As a result, materials characterised by such methods are prone to deviation from normal conditions to a great extent. To prevent this, a novel method of encapsulating sulphur particles between silicon nitride (SiN x) membranes is demonstrated in this work.

Extending the Cyclability of Alkaline Zinc-Air Batteries: Synergistic Roles of Li+ and K+ Ions in Electrodics.

Tweaking the electrolyte of the anode compartment of zinc-air battery (ZAB) system is shown to be extending the charge-discharge cyclability of the cell. An alkaline zinc (Zn)-air cell working for ∼32 h (192 cycles) without failure is extended to >55 h (>330 cycles) by modifying the anode compartment with a mixture electrolyte of KOH and LiOH. The cell containing the mixture electrolyte has a low overpotential for charging along with high discharge capacity. The role of Li+ ions in tuning the electrode morphology and electrodics is studied both theoretically and experimentally. The synergistic effect of Li+ and K+ ions in the electrolyte on improved ZAB performance is proven. This study can pave new ways for the commercial implementation of ZAB, where it has already proven its potential in low-cost, high energy density, and mobility applications.

Covalently interconnected transition metal dichalcogenide networks via defect engineering for high-performance electronic devices.

Solution-processed semiconducting transition metal dichalcogenides are at the centre of an ever-increasing research effort in printed (opto)electronics. However, device performance is limited by structural defects resulting from the exfoliation process and poor inter-flake electronic connectivity. Here, we report a new molecular strategy to boost the electrical performance of transition metal dichalcogenide-based devices via the use of dithiolated conjugated molecules, to simultaneously heal sulfur vacancies in solution-processed transition metal disulfides and covalently bridge adjacent flakes, thereby promoting percolation pathways for the charge transport. We achieve a reproducible increase by one order of magnitude in field-effect mobility (µFE), current ratio (ION/IOFF) and switching time (τS) for liquid-gated transistors, reaching 10-2 cm2 V-1 s-1, 104 and 18 ms, respectively. Our functionalization strategy is a universal route to simultaneously enhance the electronic connectivity in transition metal disulfide networks and tailor on demand their physicochemical properties according to the envisioned applications.

Large-Area Fabrication of Vertical Silicon Nanotube Arrays via Toroidal Micelle Self-Assembly.

We present a highly scalable, room-temperature strategy for fabricating vertical silicon nanotube arrays derived from a toroidal micelle pattern via a water vapor-induced block copolymer (BCP) self-assembly mechanism. A polystyrene-b-poly(ethylene oxide) (PS-b-PEO) BCP system can be self-assembled into toroidal micelle structures (diameter: 400-600 nm) on a PS-OH-modified substrate in a facile manner contrasting with other complex processes described in the literature. It was found that a minimum PS-b-PEO thickness of ∼86 nm is required for the toroidal self-assembly. Furthermore, a water vapor annealing treatment at room conditions (∼25 °C, 60 min) is shown to vastly enhance the ordering of micellar structures. A liquid-phase infiltration process was used to generate arrays of iron and nickel oxide nanorings. These oxide structures were used as templates for pattern transfer into the underlying silicon substrate via plasma etching, resulting in large-area 3D silicon nanotube arrays. The overall simplicity of this technique, as well as the wide potential versatility of the resulting metal structures, proves that such room-temperature synthesis routes are a viable pathway for complex nanostructure fabrication, with potential applicability in fields such as optics or catalysis.

Development of a Practicable Digital Pulse Read-Out for Dark-Field STEM.

When characterizing beam-sensitive materials in the scanning transmission electron microscope (STEM), low-dose techniques are essential for the reliable observation of samples in their true state. A simple route to minimize both the total electron-dose and the dose-rate is to reduce the electron beam-current and/or raster the probe at higher speeds. At the limit of these settings, and with current detectors, the resulting images suffer from unacceptable artifacts, including signal-streaking, detector-afterglow, and poor signal-to-noise ratios (SNRs). In this article, we present an alternative approach to capture dark-field STEM images by pulse-counting individual electrons as they are scattered to the annular dark-field (ADF) detector. Digital images formed in this way are immune from analog artifacts of streaking or afterglow and allow clean, high-SNR images to be obtained even at low beam-currents. We present results from both a ThermoFisher FEI Titan G2 operated at 300 kV and a Nion UltraSTEM200 operated at 200 kV, and compare the images to conventional analog recordings. ADF data are compared with analog counterparts for each instrument, a digital detector-response scan is performed on the Titan, and the overall rastering efficiency is evaluated for various scanning parameters.

Bandgap determination from individual orthorhombic thin cesium lead bromide nanosheets by electron energy-loss spectroscopy.

Inorganic lead halide perovskites are promising candidates for optoelectronic applications, due to their high photoluminescence quantum yield and narrow emission line widths. Particularly attractive is the possibility to vary the bandgap as a function of the halide composition and the size or shape of the crystals at the nanoscale. Here we present an aberration-corrected scanning transmission electron microscopy (STEM) and monochromated electron energy-loss spectroscopy (EELS) study of extended nanosheets of CsPbBr3. We demonstrate their orthorhombic crystal structure and their lateral termination with Cs-Br planes. The bandgaps are measured from individual nanosheets, avoiding the effect of the size distribution which is present in standard optical spectroscopy techniques. We find an increase of the bandgap starting at thicknesses below 10 nm, confirming the less marked effect of 1D confinement in nanosheets compared to the 3D confinement observed in quantum dots, as predicted by density functional theory calculations and optical spectroscopy data from ensemble measurements.

Comparison of Metal Adhesion Layers for Au Films in Thermoplasmonic Applications.

If thermoplasmonic applications such as heat-assisted magnetic recording are to be commercially viable, it is necessary to optimize both thermal stability and plasmonic performance of the devices involved. In this work, a variety of different adhesion layers were investigated for their ability to reduce dewetting of sputtered 50 nm Au films on SiO2 substrates. Traditional adhesion layer metals Ti and Cr were compared with alternative materials of Al, Ta, and W. Film dewetting was shown to increase when the adhesion material diffuses through the Au layer. An adhesion layer thickness of 0.5 nm resulted in superior thermomechanical stability for all adhesion metals, with an enhancement factor of up to 200× over 5 nm thick analogues. The metals were ranked by their effectiveness in inhibiting dewetting, starting with the most effective, in the order Ta > Ti > W > Cr > Al. Finally, the Au surface-plasmon polariton response was compared for each adhesion layer, and it was found that 0.5 nm adhesion layers produced the best response, with W being the optimal adhesion layer material for plasmonic performance.

MoS2 Memtransistors Fabricated by Localized Helium Ion Beam Irradiation.

Two-dimensional (2D) layered semiconductors have recently emerged as attractive building blocks for next-generation low-power nonvolatile memories. However, challenges remain in the controllable fabrication of bipolar resistive switching circuit components from these materials. Here, the experimental realization of lateral memtransistors from monolayer single-crystal molybdenum disulfide (MoS2) utilizing a focused helium ion beam is reported. Site-specific irradiation with the focused probe of a helium ion microscope creates a nanometer-scale defect-rich region, bisecting the MoS2 lattice. The reversible drift of these defects in the applied electric field modulates the resistance of the channel, enabling versatile memristive functionality. The device can reliably retain its resistance ratios and set/reset biases for 1180 switching cycles. Long-term potentiation and depression with sharp habituation are demonstrated. This work establishes the feasibility of ion irradiation for controllable fabrication of 2D memristive devices with promising key performance parameters, such as low power consumption. The applicability of these devices for synaptic emulation may address the demands of future neuromorphic architectures.

Less is More: Improved Thermal Stability and Plasmonic Response in Au Films via the Use of SubNanometer Ti Adhesion Layers.

The use of a metallic adhesion layer is known to increase the thermo-mechanical stability of Au thin films against solid-state dewetting, but in turn results in damping of the plasmonic response, reducing their utility in applications such as heat-assisted magnetic recording (HAMR). In this work, 50 nm Au films with Ti adhesion layers ranging in thickness from 0 to 5 nm were fabricated, and their thermal stability, electrical resistivity, and plasmonic response were measured. Subnanometer adhesion layers are demonstrated to significantly increase the stability of the thin films against dewetting at elevated temperatures (>200 °C), compared to more commonly used adhesion layer thicknesses that are in the range of 2-5 nm. For adhesion layers thicker than 1 nm, the diffusion of excess Ti through Au grain boundaries and subsequent oxidation was determined to result in degradation of the film. This mechanism was confirmed using transmission electron microscopy and X-ray photoelectron spectroscopy on annealed 0.5 and 5 nm adhesion layer samples. The superiority of subnanometer adhesion layers was further demonstrated through measurements of the surface-plasmon polariton resonance; those with thinner adhesion layers possessed both a stronger and spectrally sharper resonance. These results have relevance beyond HAMR to all Ti/Au systems operating at elevated temperatures.

Oxide-mediated recovery of field-effect mobility in plasma-treated MoS2.

Precise tunability of electronic properties of two-dimensional (2D) nanomaterials is a key goal of current research in this field of materials science. Chemical modification of layered transition metal dichalcogenides leads to the creation of heterostructures of low-dimensional variants of these materials. In particular, the effect of oxygen-containing plasma treatment on molybdenum disulfide (MoS2) has long been thought to be detrimental to the electrical performance of the material. We show that the mobility and conductivity of MoS2 can be precisely controlled and improved by systematic exposure to oxygen/argon plasma and characterize the material using advanced spectroscopy and microscopy. Through complementary theoretical modeling, which confirms conductivity enhancement, we infer the role of a transient 2D substoichiometric phase of molybdenum trioxide (2D-MoO x ) in modulating the electronic behavior of the material. Deduction of the beneficial role of MoO x will serve to open the field to new approaches with regard to the tunability of 2D semiconductors by their low-dimensional oxides in nano-modified heterostructures.

Direct atomic scale determination of magnetic ion partition in a room temperature multiferroic material.

The five-layer Aurivillius phase Bi6TixFeyMnzO18 system is a rare example of a single-phase room temperature multiferroic material. To optimise its properties and exploit it for future memory storage applications, it is necessary to understand the origin of the room temperature magnetisation. In this work we use high resolution scanning transmission electron microscopy, EDX and EELS to discover how closely-packed Ti/Mn/Fe cations of similar atomic number are arranged, both within the perfect structure and within defect regions. Direct evidence for partitioning of the magnetic cations (Mn and Fe) to the central three of the five perovskite (PK) layers is presented, which reveals a marked preference for Mn to partition to the central layer. We infer this is most probably due to elastic strain energy considerations. The observed increase (>8%) in magnetic cation content at the central PK layers engenders up to a 90% increase in potential ferromagnetic spin alignments in the central layer and this could be significant in terms of creating pathways to the long-range room temperature magnetic order observed in this distinct and intriguing material system.

A Deep Look Into Erionite Fibres: an Electron Microscopy Investigation of their Self-Assembly.

The exposure of humans to erionite fibres of appropriate morphology and dimension has been unambiguously linked to the occurrence of Malignant Mesothelioma. For this reason, a detailed morpho-structural investigation through Electron Microscopy techniques has been performed on erionite samples collected at two different localities, Durkee (ED) and Rome (ER), Oregon, USA. The sample from Rome has been also investigated after a prolonged leaching with Gamble's solution (ER4G) in order to evaluate the possible occurrence of morpho-structural modifications induced by this Simulated-Lung-Fluid (SLF). Here we report how the micrometric erionite fibres evolve in irregular ribbon- or rod-like bundles as a function of different nano-structural features. The reasons for the observed morphological variability have been explained by considering the structural defects located at ED surface fibrils (bi-dimensional ribbons) and the presence of nontronite, an iron-bearing clay mineral embedding the ER fibrils (mono-dimensional rods). ER4G shows a decrease in width of the rod-like fibres due to their partial digestion by SLF leaching, which synchronously dissolves nontronite. The reported results represent a valuable background toward the full comprehension of the morphological mechanisms responsible for potentially damage of lung tissue through the potential relocation of fibers to extrapulmonary sites, increasing the carcinogenic risk to humans.

Heterojunction hybrid devices from vapor phase grown MoS2.

We investigate a vertically-stacked hybrid photodiode consisting of a thin n-type molybdenum disulfide (MoS2) layer transferred onto p-type silicon. The fabrication is scalable as the MoS2 is grown by a controlled and tunable vapor phase sulfurization process. The obtained large-scale p-n heterojunction diodes exhibit notable photoconductivity which can be tuned by modifying the thickness of the MoS2 layer. The diodes have a broad spectral response due to direct and indirect band transitions of the nanoscale MoS2. Further, we observe a blue-shift of the spectral response into the visible range. The results are a significant step towards scalable fabrication of vertical devices from two-dimensional materials and constitute a new paradigm for materials engineering.

Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids.

To progress from the laboratory to commercial applications, it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene. Here we show that high-shear mixing of graphite in suitable stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. X-ray photoelectron spectroscopy and Raman spectroscopy show the exfoliated flakes to be unoxidized and free of basal-plane defects. We have developed a simple model that shows exfoliation to occur once the local shear rate exceeds 10(4) s(-1). By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from hundreds of millilitres up to hundreds of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals.