In Situ Observation of Low-Power Nano-Synaptic Response in Graphene Oxide Using Conductive Atomic Force Microscopy.

Multiple studies have reported the observation of electro-synaptic response in different metal/insulator/metal devices. However, most of them analyzed large (>1 µm2 ) devices that do not meet the integration density required by industry (1010  devices/mm2 ). Some studies emploied a scanning tunneling microscope (STM) to explore nano-synaptic response in different materials, but in this setup there is a nanogap between the insulator and one of the metallic electrodes (i.e., the STM tip), not present in real devices. Here, it is demonstrated how to use conductive atomic force microscopy to explore the presence and quality of nano-synaptic response in confined areas <50 nm2 . Graphene oxide (GO) is selected due to its easy fabrication. Metal/GO/metal nano-synapses exhibit potentiation and paired pulse facilitation with low write current levels <1 µA (i.e., power consumption ≈3 µW), controllable excitatory post-synaptic currents, and long-term potentiation and depression. The results provide a new method to explore nano-synaptic plasticity at the nanoscale, and point to GO as an important candidate for the fabrication of ultrasmall (<50 nm2 ) electronic synapses fulfilling the integration density requirements of neuromorphic systems.

Charged Carbon Nanomaterials: Redox Chemistries of Fullerenes, Carbon Nanotubes, and Graphenes.

Since the discovery of buckminsterfullerene over 30 years ago, sp2-hybridised carbon nanomaterials (including fullerenes, carbon nanotubes, and graphene) have stimulated new science and technology across a huge range of fields. Despite the impressive intrinsic properties, challenges in processing and chemical modification continue to hinder applications. Charged carbon nanomaterials (CCNs), formed via the reduction or oxidation of these carbon nanomaterials, facilitate dissolution, purification, separation, chemical modification, and assembly. This approach provides a compelling alternative to traditional damaging and restrictive liquid phase exfoliation routes. The broad chemistry of CCNs not only provides a versatile and potent means to modify the properties of the parent nanomaterial but also raises interesting scientific issues. This review focuses on the fundamental structural forms: buckminsterfullerene, single-walled carbon nanotubes, and single-layer graphene, describing the generation of their respective charged nanocarbon species, their interactions with solvents, chemical reactivity, specific (opto)electronic properties, and emerging applications.

Unweaving the rainbow: a review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity.

Single-walled carbon nanotubes (SWNTs) are a fundamental family of distinct molecules, each bearing the possibility of different reactivities due to their intrinsically distinct chemical properties. SWNT syntheses generate a heterogeneous mixture of species with varying electronic character, lengths, diameters and helicities, (n,m), as well as other amorphous, graphitic and metal catalyst impurities. In recent years, selective syntheses and post-synthetic separation strategies have advanced, driven by the requirement for pure SWNTs displaying particular features. Covalent surface modifications are widely-used to adapt SWNTs for specific applications with modified solubility, compatibility and specific functionalities. In many cases, such reactions have been found to be selective, illuminating the fundamentally distinct chemistry of each (n,m) species. This differential reactivity has found immediate utility in facilitating the sorting of nanotubes according to specific diameter, electronic properties and, most importantly, helicity. In this tutorial review, we discuss a wide range of selective reactions, the mechanisms that are thought to govern selectivity, and the challenges of separating, characterising and regenerating the modified SWNTs.

Determining the Level and Location of Functional Groups on Few-Layer Graphene and Their Effect on the Mechanical Properties of Nanocomposites.

Graphene is a highly desirable material for a variety of applications; in the case of nanocomposites, it can be functionalized and added as a nanofiller to alter the ultimate product properties, such as tensile strength. However, often the material properties of the functionalized graphene and the location of any chemical species, attached via different functionalization processes, are not known. Thus, it is not necessarily understood why improvements in product performance are achieved, which hinders the rate of product development. Here, a commercially available powder containing few-layer graphene (FLG) flakes is characterized before and after plasma or chemical functionalization with either nitrogen or oxygen species. A range of measurement techniques, including tip-enhanced Raman spectroscopy (TERS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and NanoSIMS, were used to examine the physical and chemical changes in the FLG material at both the micro- and nanoscale. This is the first reported TERS imaging of commercially available FLG flakes of submicron lateral size, revealing the location of the defects (edge versus basal plane) and variations in the level of functionalization. Graphene-polymer composites were then produced, and the dispersion of the graphitic material in the matrix was visualized using ToF-SIMS. Finally, mechanical testing of the composites demonstrated that the final product performance could be enhanced but differed depending on the properties of the original graphitic material.

Core-Shell Electrospun Polycrystalline ZnO Nanofibers for Ultra-Sensitive NO2 Gas Sensing.

This Research Article discusses the growth of polycrystalline, self-supporting ZnO nanofibers, which can detect nitrogen dioxide (NO2) gas down to 1 part per billion (ppb), one of the smallest detection limits reported for NO2 using ZnO. A new and innovative method has been developed for growing polycrystalline ZnO nanofibers. These nanofibers have been created using core-shell electrospinning of inorganic metal precursor zinc neodecanoate, where growth occurs at the core of the nanofibers. This process produces contamination-free, self-supporting, polycrystalline ZnO nanofibers of an average diameter and grain size 50 and 8 nm, respectively, which are ideal for gas sensing applications. This process opens up an exciting opportunity for creating nanofibers from a variety of metal oxides, facilitating many new applications especially in the areas of sensors and wearable technologies.

Chemical routes to discharging graphenides.

Chemical and electrochemical reduction methods allow the dispersion, processing, and/or functionalization of discrete sp2-hybridised nanocarbons, including fullerenes, nanotubes and graphenes. Electron transfer to the nanocarbon raises the Fermi energy, creating nanocarbon anions and thereby activating an array of possible covalent reactions. The Fermi level may then be partially or fully lowered by intended functionalization reactions, but in general, techniques are required to remove excess charge without inadvertent covalent reactions that potentially degrade the nanocarbon properties of interest. Here, simple and effective chemical discharging routes are demonstrated for graphenide polyelectrolytes and are expected to apply to other systems, particularly nanotubides. The discharging process is inherently linked to the reduction potentials of such chemical discharging agents and the unusual fundamental chemistry of charged nanocarbons.

Enhanced piezoelectric effect at the edges of stepped molybdenum disulfide nanosheets.

The development of piezoelectric layered materials may be one of the key elements enabling expansion of nanotechnology, as they offer a solution for the construction of efficient transducers for a wide range of applications, including self-powered devices. Here, we investigate the piezoelectric effect in multilayer (ML) stepped MoS2 flakes obtained by liquid-phase exfoliation, which is especially interesting because it may allow the scalable fabrication of electronic devices using large area deposition techniques (e.g. solution casting, spray coating, inkjet printing). By using a conductive atomic force microscope we map the piezoelectricity of the MoS2 flakes at the nanoscale. Our experiments demonstrate the presence of electrical current densities above 100 A cm-2 when the flakes are strained in the absence of bias, and the current increases proportional to the bias. Simultaneously collected topographic and current maps demonstrate that the edges of stepped ML MoS2 flakes promote the piezoelectric effect, where the largest currents are observed. Density functional theory calculations are consistent with the ring-like piezoelectric potential generated when the flakes are strained, as well as the enhanced piezoelectric effect at edges. Our results pave the way to the design of piezoelectric devices using layered materials.

Ionic solutions of two-dimensional materials.

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

Microfluidization of Graphite and Formulation of Graphene-Based Conductive Inks.

We report the exfoliation of graphite in aqueous solutions under high shear rate [∼ 108 s-1] turbulent flow conditions, with a 100% exfoliation yield. The material is stabilized without centrifugation at concentrations up to 100 g/L using carboxymethylcellulose sodium salt to formulate conductive printable inks. The sheet resistance of blade coated films is below ∼2Ω/□. This is a simple and scalable production route for conductive inks for large-area printing in flexible electronics.

Carbon nanotube anions for the preparation of gold nanoparticle-nanocarbon hybrids.

Gold nanoparticles (AuNPs) can be evenly deposited on single-walled carbon nanotubes (SWCNTs) via the reduction of the highly stable complex, chloro(triphenylphosphine) gold(I), with SWCNT anions ('nanotubides'). This methodology highlights the unusual chemistry of nanotubides and provides a blueprint for the generation of many other hybrid nanomaterials.

Probing the charging mechanisms of carbon nanomaterial polyelectrolytes.

Chemical charging of single-walled carbon nanotubes (SWCNTs) and graphenes to generate soluble salts shows great promise as a processing route for electronic applications, but raises fundamental questions. The reduction potentials of highly-charged nanocarbon polyelectrolyte ions were investigated by considering their chemical reactivity towards metal salts/complexes in forming metal nanoparticles. The redox activity, degree of functionalisation and charge utilisation were quantified via the relative metal nanoparticle content, established using thermogravimetric analysis (TGA), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and X-ray photoelectron spectroscopy (XPS). The fundamental relationship between the intrinsic nanocarbon electronic density of states and Coulombic effects during charging is highlighted as an important area for future research.

Electrochemical processing of discrete single-walled carbon nanotube anions.

The dissolution of single-walled carbon nanotubes (SWCNTs) remains a fundamental challenge, reliant on aggressive chemistry or ultrasonication and lengthy ultracentrifugation. In contrast, simple nonaqueous electrochemical reduction leads to spontaneous dissolution of individualized SWCNTs from raw, unprocessed powders. The intrinsic electrochemical stability and conductivity of these nanomaterials allow their electrochemical dissolution from a pure SWCNT cathode to form solutions of individually separate and distinct (i.e., discrete) nanotube anions with varying charge density. The integrity of the SWCNT sp² framework during the charge/discharge process is demonstrated by optical spectroscopy data. Other than a reversible change in redox/solvation state, there is no obvious chemical functionalization of the structure, suggesting an analogy to conventional atomic electrochemical dissolution. The heterogeneity of as-synthesized SWCNT samples leads to the sequential dissolution of distinct fractions over time, with fine control over the electrochemical potential. Initial preferential dissolution of defective nanotubes and carbonaceous debris provides a simple, nondestructive means to purify raw materials without recourse to the usual, damaging, competitive oxidation reactions. Neutral SWCNTs can be recovered either by electroplating at an anode or by reaction with a suitable electrophile.

Giant cationic polyelectrolytes generated via electrochemical oxidation of single-walled carbon nanotubes.

Previously, reduced single-walled carbon nanotube anions have been used for effective processing and functionalization. Here we report individually separate and distinct (that is, discrete) single-walled carbon nanotube cations, directly generated from a pure anode using a non-aqueous electrochemical technique. Cyclic voltammetry provides evidence for the reversibility of this nanoion electrochemisty, and can be related to the complex electronic density of states of the single-walled carbon nanotubes. Fixed potentiostatic oxidation allows spontaneous dissolution of nanotube cations ('nanotubium'); Raman spectroscopy and transmission electron microscopy show that sequential fractions are purified, separating amorphous carbon and short, defective single-walled carbon nanotubes, initially. The preparation of nanotubium, in principle, enables a new family of nucleophilic grafting reactions for single-walled carbon nanotubes, exploited here, to assemble nanotubes on amine-modified Si surfaces. Other nanoparticle polyelectrolyte cations may be anticipated.