Mesoscopic 3D Charge Transport in Solution-Processed Graphene-Based Thin Films: A Multiscale Analysis

Graphene and related 2D material (GRM) thin films consist of 3D assembly of billions of 2D nanosheets randomly distributed and interacting via van der Waals forces. Their complexity and the multiscale nature yield a wide variety of electrical characteristics ranging from doped semiconductor to glassy metals depending on the crystalline quality of the nanosheets, their specific structural organization ant the operating temperature. Here, the charge transport (CT) mechanisms are studied that are occurring in GRM thin films near the metal-insulator transition (MIT) highlighting the role of defect density and local arrangement of the nanosheets. Two prototypical nanosheet types are compared, i.e., 2D reduced graphene oxide and few-layer-thick electrochemically exfoliated graphene flakes, forming thin films with comparable composition, morphology and room temperature conductivity, but different defect density and crystallinity. By investigating their structure, morphology, and the dependence of their electrical conductivity on temperature, noise and magnetic-field, a general model is developed describing the multiscale nature of CT in GRM thin films in terms of hopping among mesoscopic bricks, i.e., grains. The results suggest a general approach to describe disordered van der Waals thin films

Creating and Using Learning Objects in Qualitative Research Education

Based upon the lessons learned and the educational materials generated from a doctoral course on qualitative data analysis, a group of doctoral students, their professor, and a linguistics consultant launched an on- going project to create a series of reusable learning objects designed to help other groups of students and professors learn how to analyze qualitative data. The results of the first six months of this project are shared, as the team describes how they have begun to use instructional design and software applications to create a digital learning environment in the form of a series of activities engineered to help analysts learn how to master grounded theory open codin

Structure and dynamics of pentacene on SiO2: From monolayer to bulk structure

We have used confocal micro Raman spectroscopy, atomic force microscopy (AFM), and x-ray diffraction (XRD) to investigate pentacene films obtained by vacuum deposition on SiO2 substrates. These methods allow us to follow the evolution of lattice structure, vibrational dynamics, and crystal morphology during the growth from monolayer, to TF, and, finally, to bulk crystal. The Raman measurements, supported by the AFM and XRD data, indicate that the film morphology depends on the deposition rate. High deposition rates yield two-dimensional nucleation and quasi-layer-by-layer growth of the T-F form only. Low rates yield three-dimensional nucleation and growth, with phase mixing occurring in sufficiently thick films, where the T-F form is accompanied by the "high-temperature" bulk phase. Our general findings are consistent with those of previous work. However, the Raman measurements, supported by lattice dynamics calculations, provide additional insight into the nature of the TFs, showing that their characteristic spectra originate from a loss of dynamical correlation between adjacent layers

Benchmarking of graphene-based materials: Real commercial products versus ideal graphene

There are tens of industrial producers claiming to sell graphene and related materials (GRM), mostly as solid powders. Recently the quality of commercial GRM has been questioned, and procedures for GRM quality control were suggested using Raman Spectroscopy or Atomic Force Microscopy. Such techniques require dissolving the sample in solvents, possibly introducing artefacts. A more pragmatic approach is needed, based on fast measurements and not requiring any assumption on GRM solubility. To this aim, we report here an overview of the properties of commercial GRM produced by selected companies in Europe, USA and Asia. We benchmark: (A) size, (B) exfoliation grade and (C) oxidation grade of each GRM versus the ones of \u27ideal\u27 graphene and, most importantly, versus what reported by the producer. In contrast to previous works, we report explicitly the names of the GRM producers and we do not re-dissolve the GRM in solvents, but only use techniques compatible with industrial powder metrology. A general common trend is observed: Products having low defectivity (%sp 2 bonds >95%) feature low surface area (<200 m 2 g -1 ), while highly exfoliated GRM show a lower sp 2 content, demonstrating that it is still challenging to exfoliate GRM at industrial level without adding defects

Discovery of Volatile Biomarkers of Parkinson’s Disease from Sebum

Parkinson's disease (PD) is a progressive, neurodegenerative disease that presents with significant motor symptoms, for which there is no diagnostic chemical test. We have serendipitously identified a hyperosmic individual, a "Super Smeller" who can detect PD by odor alone, and our early pilot studies have indicated that the odor was present in the sebum from the skin of PD subjects. Here, we have employed an unbiased approach to investigate the volatile metabolites of sebum samples obtained noninvasively from the upper back of 64 participants in total (21 controls and 43 PD subjects). Our results, validated by an independent cohort (n=31), identified a distinct volatiles-associated signature of PD, including altered levels of perillic aldehyde and eicosane, the smell of which was then described as being highly similar to the scent of PD by our "Super Smeller"

Electrical percolation in graphene-polymer composites

Electrically conductive composites comprising polymers and graphene are extremely versatile and have a wide range of potential applications. The conductivity of these composites depends on the choice of polymer matrix, the type of graphene filler, the processing methodology, and any post-production treatments. In this review, we discuss the progress in graphene-polymer composites for electrical applications. Graphene filler types are reviewed, the progress in modelling these composites is outlined, the current optimal composites are presented, and the example of strain sensors is used to demonstrate their application

Degradation behaviors and mechanisms of MoS2 crystals relevant to bioabsorbable electronics

Monolayer molybdenum disulfide (MoS2) exhibits unique semiconducting and bioresorption properties, giving this material enormous potential for electronic/biomedical applications, such as bioabsorbable electronics. In this regard, understanding the degradation performance of monolayer MoS2 in biofluids allows modulation of the properties and lifetime of related bioabsorbable devices and systems. Herein, the degradation behaviors and mechanisms of monolayer MoS2 crystals with different misorientation angles are explored. High-angle grain boundaries (HAGBs) biodegrade faster than low-angle grain boundaries (LAGBs), exhibiting degraded edges with wedge and zigzag shapes, respectively. Triangular pits that formed in the degraded grains have orientations opposite to those of the parent crystals, and these pits grow into larger pits laterally. These behaviors indicate that the degradation is induced and propagated based on intrinsic defects, such as grain boundaries and point defects, because of their high chemical reactivity due to lattice breakage and the formation of dangling bonds. High densities of dislocations and point defects lead to high chemical reactivity and faster degradation. The structural cause of MoS2 degradation is studied, and a feasible approach to study changes in the properties and lifetime of MoS2 by controlling the defect type and density is presented. The results can thus be used to promote the widespread use of two-dimensional materials in bioabsorption applications

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Space Charge at Nanoscale: Probing Injection and Dynamic Phenomena Under Dark/Light Configurations by Using KPFM and C-AFM

International audienc