Will Gannett

Determination of the Local Chemical Structure of Graphene Oxide and Reduced Graphene Oxide

www.MaterialsViews.com C O M M Determination of the Local Chemical Structure of Graphene Oxide and Reduced Graphene Oxide U N IC A By Kris Erickson , Rolf Erni , Zonghoon Lee , Nasim Alem , Will Gannett , and Alex Zettl * IO N Although the unique electronic and mechanical properties of graphene suggest numerous intriguing applications, the requisite large-scale direct synthesis and solution-based handling have proven diffi cult. [ 1 , 2 ] It has been suggested that a functionalized form of graphene, graphene oxide (GO), could provide a solution-friendly route to facile, high-throughput graphene manipulation. [ 2 ] For such a route to be viable, however, GO must be convertible back to graphene, ostensibly via chemical reduction and thermal annealing. Unfortunately, transport measurements indicate that the reconstituted material, reduced and annealed graphene oxide (raGO), has electrical conductivity orders of magnitude lower than that of graphene. [ 2 , 3 ] This raises the question: can oxidized graphene be effectively converted back to graphene, and if not, what can it be converted to? Central to this question are the detailed atomic structures of GO and raGO, which, despite their importance, remain largely unknown. [ 4 ] We present here ultra-high-resolution transmission electron microscopy (TEM) images and dynamics studies of suspended sheets of graphene, GO, and raGO, obtained using aberration-corrected instrumentation. It should be noted that both the label GO and raGO (also referred to as “chemically converted graphene”) [ 5 ] refer to a wide variety of materials with the properties of each material being largely dependent upon the particular synthetic route employed. This study presents one particular synthetic method for GO and raGO. Among the various methods possible for synthesizing GO and raGO, we followed methods which have yielded the highest reported fi nal conductivities, as this material would be most suitable as a potential graphene alternative. [ 2 , 6–11 ] The local and global structure and stability of GO and raGO are revealed. We fi nd that the raGO material under study is greatly structurally dissimilar to graphene, being unstable under signifi cant electron beam

Tunable Phonon Polaritons in Atomically Thin van der Waals Crystals of Boron Nitride

Nanoimaged Polaritons Engineered heterostructures consisting of thin, weakly bound layers can exhibit many attractive electronic properties. Dai et al. (p. 1125) used infrared nanoimaging on the surface of hexagonal boron nitride crystals to detect phonon polaritons, collective modes that originate in the coupling of photons to optical phonons. The findings reveal the dependence of the polariton wavelength and dispersion on the thickness of the material down to just a few atomic layers. Infrared nanoimaging is used to detect a type of surface collective mode in a representative van der Waals crystal. van der Waals heterostructures assembled from atomically thin crystalline layers of diverse two-dimensional solids are emerging as a new paradigm in the physics of materials. We used infrared nanoimaging to study the properties of surface phonon polaritons in a representative van der Waals crystal, hexagonal boron nitride. We launched, detected, and imaged the polaritonic waves in real space and altered their wavelength by varying the number of crystal layers in our specimens. The measured dispersion of polaritonic waves was shown to be governed by the crystal thickness according to a scaling law that persists down to a few atomic layers. Our results are likely to hold true in other polar van der Waals crystals and may lead to new functionalities.

Graphene as a Long-Term Metal Oxidation Barrier: Worse Than Nothing

Anticorrosion and antioxidation surface treatments such as paint or anodization are a foundational component in nearly all industries. Graphene, a single-atom-thick sheet of carbon with impressive impermeability to gases, seems to hold promise as an effective anticorrosion barrier, and recent work supports this hope. We perform a complete study of the short- and long-term performance of graphene coatings for Cu and Si substrates. Our work reveals that although graphene indeed offers effective short-term oxidation protection, over long time scales it promotes more extensive wet corrosion than that seen for an initially bare, unprotected Cu surface. This surprising result has important implications for future scientific studies and industrial applications. In addition to informing any future work on graphene as a protective coating, the results presented here have implications for graphenes performance in a wide range of applications.

Multiply folded graphene

The folding of paper, hide, and woven fabric has been used for millennia to achieve enhanced articulation, curvature, and visual appeal for intrinsically flat, two-dimensional materials. For graphene, an ideal twodimensional material, folding may transform it to complex shapes with new and distinct properties. Here, we present experimental results that folded structures in graphene, termed grafold, exist, and their formations can be controlled by introducing anisotropic surface curvature during graphene synthesis or transfer processes. Using pseudopotential-density-functional-theory calculations, we also show that double folding modifies the electronic band structure of graphene. Furthermore, we demonstrate the intercalation of C60 into the grafolds. Intercalation or functionalization of the chemically reactive folds further expands grafold’s mechanical, chemical, optical, and electronic diversity.

Subnanometer Vacancy Defects Introduced on Graphene by Oxygen Gas

The basal plane of graphene has been known to be less reactive than the edges, but some studies observed vacancies in the basal plane after reaction with oxygen gas. Observation of these vacancies has typically been limited to nanometer-scale resolution using microscopic techniques. This work demonstrates the introduction and observation of subnanometer vacancies in the basal plane of graphene by heat treatment in a flow of oxygen gas at low temperature such as 533 K or lower. High-resolution transmission electron microscopy was used to directly observe vacancy structures, which were compared with image simulations. These proposed structures contain C═O, pyran-like ether, and lactone-like groups.

Screening-Engineered Field-Effect Solar Cells

Photovoltaics (PV) are a promising source of clean renewable energy, but current technologies face a cost-to-efficiency trade-off that has slowed widespread implementation. We have developed a PV architecture-screening-engineered field-effect photovoltaics (SFPV)-that in principle enables fabrication of low-cost, high efficiency PV from virtually any semiconductor, including the promising but hard-to-dope metal oxides, sulfides, and phosphides. Prototype SFPV devices have been constructed and are found to operate successfully in accord with model predictions.

Surface Atom Motion to Move Iron Nanocrystals through Constrictions in Carbon Nanotubes under the Action of an Electric Current

Under the application of electrical currents, metal nanocrystals inside carbon nanotubes can be bodily transported. We examine experimentally and theoretically how an iron nanocrystal can pass through a constriction in the carbon nanotube with a smaller cross-sectional area than the nanocrystal itself. Remarkably, through in situ transmission electron imaging and diffraction, we find that, while passing through a constriction, the nanocrystal remains largely solid and crystalline and the carbon nanotube is unaffected. We account for this behavior by a pattern of iron atom motion and rearrangement on the surface of the nanocrystal. The nanocrystal motion can be described with a model whose parameters are nearly independent of the nanocrystal length, area, temperature, and electromigration force magnitude. We predict that metal nanocrystals can move through complex geometries and constrictions, with implications for both nanomechanics and tunable synthesis of metal nanoparticles.

A proposed measurement of controlled defect induction and annealing in a carbon nanotube

We propose controlled creation and annealing of defects in carbon nanotubes by plasma and current application, respectively. TEM is used to map nanoparticles, which nucleate at defect sites and act as position markers.