Investigating the thermal stability of metallic and non-metallic nanoparticles using a novel graphene oxide-based transmission electron microscopy heating-membrane.

In recent years, graphene has been explored as a heating membrane for studying high-temperature dynamics inside the transmission electron microscope (TEM) due to several limitations with the existing silicon nitride-based membrane. However, the transfer of monolayer graphene films for TEM experiments is challenging and requires many complicated steps with a minimum success rate. This work developed a novelin situheating platform by combining the graphene oxide (GO) flakes in the pre-patterned chips. The isolated GO flake was self-suspended between the metal electrodes by a simple drop-casting process. The GO was reduced and characterized using Raman and electron energy-loss spectroscopy. Furthermore, a GO-based heater was used to investigate the thermal stability of gold and silica nanoparticles. The gold nanoparticles evaporated non-uniformly and left an empty carbon shell, while silica disappeared uniformly by etching carbon support. We successfully demonstrated a GO flake as a heating membrane to study high temperature thermal dynamic reactions: melting/evaporation, agglomeration, Rayleigh instability, and formation/or removal of carbon in the nanoparticles.

Can a Procedure for the Growth of Single-layer Graphene on Copper be used in Different Chemical Vapor Deposition Reactors?

In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a "showerhead" cold-wall type, whereas the other represented the popular "tubular" hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm2 -scale SLG growth that differed only by the carrier gas flow rate used in the two reactors.

Paper-Based In-Situ Gold Nanoparticle Synthesis for Colorimetric, Non-Enzymatic Glucose Level Determination.

Due to its properties, paper represents an alternative to perform point-of-care tests for colorimetric determination of glucose levels, providing simple, rapid, and inexpensive means of diagnosis. In this work, we report the development of a novel, rapid, disposable, inexpensive, enzyme-free, and colorimetric paper-based assay for glucose level determination. This sensing strategy is based on the synthesis of gold nanoparticles (AuNPs) by reduction of a gold salt precursor, in which glucose acts simultaneously as reducing and capping agent. This leads to a direct measurement of glucose without any enzymes or depending on the detection of intermediate products as in conventional enzymatic colorimetric methods. Firstly, we modelled the synthesis reaction of AuNPs to determine the optical, morphological, and kinetic properties and their manipulation for glucose sensing, by determining the influence of each of the reaction precursors towards the produced AuNPs, providing a guide for the manipulation of nucleation and growth. The adaptation of this synthesis into the developed paper platform was tested and calibrated using different standard solutions with physiological concentrations of glucose. The response of the colorimetric signals obtained with this paper-based platform showed a linear behavior until 20 mM, required for glycemic control in diabetes, using the Red × Value/Grey feature combination as a calibration metric, to describe the variations in color intensity and hue in the spot test zone. The colorimetric sensor revealed a detection limit of 0.65 mM, depending on calibration metric and sensitivity of 0.013 AU/mM for a linear sensitivity range from 1.25 to 20 mM, with high specificity for the determination of glucose in complex standards with other common reducing interferents and human serum.

Current-Induced Helicity Reversal of a Single Skyrmionic Bubble Chain in a Nanostructured Frustrated Magnet.

Helicity indicates the in-plane magnetic-moment swirling direction of a skyrmionic configuration. The ability to reverse the helicity of a skyrmionic bubble via purely electrical means has been predicted in frustrated magnetic systems; however, it has been challenging to observe this experimentally. The current-driven helicity reversal of the skyrmionic bubble in a nanostructured frustrated Fe3 Sn2 magnet is experimentally demonstrated. The critical current density required to trigger the helicity reversal is 109 -1010 A m-2 , with a corresponding pulse-width varying from 1 µs to 100 ns. Computational simulations reveal that both the pinning effect and dipole-dipole interaction play a crucial role in the helicity reversal process.

Chemical and Structural Analysis of Carbon Materials Subjected to Alkaline Oxidation.

Redox species such as transition metals may, unknowingly, integrate carbon materials that are produced (or supplied) for the assembling of electrodes in batteries, supercapacitors, and fuel cells. The extent to which these species alter the electrochemical profile of carbons and affect the performance and/or degradation of energy storage systems is still not fully appreciated. Alkaline oxidation (or fusion) is a promising approach to disintegrate nanocarbons for the subsequent study of their chemical composition by routine analytical tools. In this work, three commercial carbon powders, relevant for electrochemical applications and bearing varied textural orientation (point, radial, and planar), were selected to evaluate the versatility of fusion as a pretreatment process for elemental analysis. Additionally, the interaction of the flux, a lithium borate salt, with the carbons was elucidated by examining their post-fusion residues. The degree of structural degradation varied and, generally, the doping with Li and/or B (whether substitutional or interstitial) was low to nonexistent. With future developments, fusion could become a relevant pretreatment method to analyze the composition of carbon materials, even when complex mixtures (e.g., cycled battery electrodes) and larger batch scales are considered.

Current-induced restructuring in bent silver nanowires.

A number of metallic one-dimensional nanostructures have been proposed as interconnects for next-generation electronic devices. Generally, reports on charge transport properties consider low current density regimes in nanowires (or nanotubes) with intrinsically straight configurations. In these circumstances, direct observations of the interconnecting nanofilament electrical failure are scarce, particularly for initially crooked structures. Here, the electrical and structural responses of suspended silver nanowires exposed to increasing current densities were analysed using in situ transmission electron microscopy. At low rates of bias application, initially straight nanowires showed trivial behaviour up to their breakdown, with electromigration and gradual necking taking place. By contrast, these nanowires with an initially crooked configuration exhibit a mixed set of responses which included string-like resonance and structural rearrangements. Remarkably, it was observed that restructuring does not necessarily compromise the transport function of these interconnectors. Hence, initially crooked nanowires could import higher resilience to future nanoelectronic devices by delaying catastrophic breakdown of interconnectors subjected to unexpected current surges.

Cobalt ferrite supported on reduced graphene oxide as a T 2 contrast agent for magnetic resonance imaging.

Nanoscaled spinel-structured ferrites bear promise as next-generation contrast agents for magnetic resonance imaging. However, the small size of the particles commonly leads to colloidal instability under physiological conditions. To circumvent this problem, supports onto which the dispersed nanoparticles can be anchored have been proposed. Amongst these, flakes of graphene have shown interesting performance but it remains unknown if and how their surface texture and chemistry affect the magnetic properties and relaxation time (T 2) of the ferrite nanoparticles. Here, it is shown that the type of graphene oxide (GO) precursor, used to make composites of cobalt ferrite (CoFe2O4) and reduced GO, influences greatly not just the T 2 but also the average size, dispersion and magnetic behaviour of the grafted nanoparticles. Accordingly, and without compromising biocompatibility, a judicious choice of the initial GO precursor can result in the doubling of the proton relaxivity rate in this system.

Elemental Quantification and Residues Characterization of Wet Digested Certified and Commercial Carbon Materials.

Inductively coupled plasma optical emission spectroscopy (ICP-OES) is a common, relatively low cost, and straightforward analytical technique for the study of trace quantities of metals in solid materials, but its applicability to nanocarbons (e.g., graphene and nanotubes) has suffered from the lack of efficient digestion steps and certified reference materials (CRM). Here, various commercial and certified graphitic carbon materials were subjected to a "two-step" microwave-assisted acid digestion procedure, and the concentrations of up to 18 elements were analyzed by ICP-OES. With one exception (Sm), successful quantification of all certified elements in the two reference nanocarbons studied was achieved, hence validating the sample preparation approach used. The applicability of our "two-step" protocol was further confirmed for a commercial single-walled carbon nanotube sample. However, the digestion was markedly incomplete for all other commercial materials tested. Where possible, the digestion residues of the carbon materials analyzed (CRM included) were characterized to understand the structural changes that take place and how this may explain the challenge of disintegrating graphitic carbon. In this respect, it was found that solid state nuclear magnetic resonance holds considerable promise as a nonlocalized, easily interpretable, and reliable tool to access the efficient disintegration of these materials.

Structural and chemical analysis of gadolinium halides encapsulated within WS2 nanotubes.

The hollow cavities of nanotubes serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of WS2 nanotubes by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is non-trivial due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

Structural changes of electron and ion beam-deposited contacts in annealed carbon-based electrical devices.

The use of electron and ion beam deposition to make devices containing discrete nanostructures as interconnectors is a well-known nanofabrication process. Classically, one-dimensional materials such as carbon nanotubes (CNTs) have been electrically characterized by resorting to these beam deposition methods. While much attention has been given to the interconnectors, less is known about the contacting electrodes (or leads). In particular, the structure and chemistry of the electrode-interconnector interface is a topic that deserves more attention, as it is critical to understand the device behavior. Here, the structure and chemistry of Pt electrodes, deposited either with electron or ion beams and contacted to a CNT, are analyzed before and after thermally annealing the device in a vacuum. Free-standing Pt nanorods, acting as beam-deposited electrode models, are also characterized pre- and post-annealing. Overall, the as-deposited leads contain a non-negligible amount of amorphous carbon that is consolidated, upon heating, as a partially graphitized outer shell enveloping a Pt core. This observation raises pertinent questions regarding the definition of electrode-nanostructure interfaces in electrical devices, in particular long-standing assumptions of metal-CNT contacts fabricated by direct beam deposition methods.