Sandeep Gorantla

van der Waals epitaxial growth of graphene on sapphire by chemical vapor deposition without a metal catalyst.

van der Waals epitaxial growth of graphene on c-plane (0001) sapphire by CVD without a metal catalyst is presented. The effects of CH(4) partial pressure, growth temperature, and H(2)/CH(4) ratio were investigated and growth conditions optimized. The formation of monolayer graphene was shown by Raman spectroscopy, optical transmission, grazing incidence X-ray diffraction (GIXRD), and low voltage transmission electron microscopy (LVTEM). Electrical analysis revealed that a room temperature Hall mobility above 2000 cm(2)/V·s was achieved, and the mobility and carrier type were correlated to growth conditions. Both GIXRD and LVTEM studies confirm a dominant crystal orientation (principally graphene [10-10] || sapphire [11-20]) for about 80-90% of the material concomitant with epitaxial growth. The initial phase of the nucleation and the lateral growth from the nucleation seeds were observed using atomic force microscopy. The initial nuclei density was ~24 μm(-2), and a lateral growth rate of ~82 nm/min was determined. Density functional theory calculations reveal that the binding between graphene and sapphire is dominated by weak dispersion interactions and indicate that the epitaxial relation as observed by GIXRD is due to preferential binding of small molecules on sapphire during early stages of graphene formation.

Rolled-up nanomembranes as compact 3D architectures for field effect transistors and fluidic sensing applications.

We fabricate inorganic thin film transistors with bending radii of less than 5 μm maintaining their high electronic performance with on-off ratios of more than 10(5) and subthreshold swings of 160 mV/dec. The fabrication technology relies on the roll-up of highly strained semiconducting nanomembranes, which compacts planar transistors into three-dimensional tubular architectures opening intriguing potential for microfluidic applications. Our technique probes the ultimate limit for the bending radius of high performance thin film transistors.

Programmable Sub-nanometer Sculpting of Graphene with Electron Beams

Electron beams in transmission electron microscopes are very attractive to engineer and pattern graphene toward all-carbon device fabrication. The use of condensed beams typically used for sequential raster imaging is particularly exciting since they potentially provide high degrees of precision. However, technical difficulties, such as the formation of electron beam induced deposits on sample surfaces, have hindered the development of this technique. We demonstrate how one can successfully use a condensed electron beam, either with or without C(s) correction, to structure graphene with sub-nanometer precision in a programmable manner. We further demonstrate the potential of the developed technique by combining it with an established route to engineer graphene nanoribbons to single-atom carbon chains.

Low Voltage Transmission Electron Microscopy of Graphene

The initial isolation of graphene in 2004 spawned massive interest in this two-dimensional pure sp(2) carbon structure due to its incredible electrical, optical, mechanical, and thermal effects. This in turn led to the rapid development of various characterization tools for graphene. Examples include Raman spectroscopy and scanning tunneling microscopy. However, the one tool with the greatest prowess for characterizing and studying graphene is the transmission electron microscope. State-of-the-art (scanning) transmission electron microscopes enable one to image graphene with atomic resolution, and also to conduct various other characterizations simultaneously. The advent of aberration correctors was timely in that it allowed transmission electron microscopes to operate with reduced acceleration voltages, so that damage to graphene is avoided while still providing atomic resolution. In this comprehensive review, a brief introduction is provided to the technical aspects of transmission electron microscopes relevant to graphene. The reader is then introduced to different specimen preparation techniques for graphene. The different characterization approaches in both transmission electron microscopy and scanning transmission electron microscopy are then discussed, along with the different aspects of electron diffraction and electron energy loss spectroscopy. The use of graphene for other electron microscopy approaches such as in-situ investigations is also presented.

Stranski–Krastanov and Volmer–Weber CVD Growth Regimes To Control the Stacking Order in Bilayer Graphene

Aside from unusual properties of monolayer graphene, bilayer has been shown to have even more interesting physics, in particular allowing bandgap opening with dual gating for proper interlayer symmetry. Such properties, promising for device applications, ignited significant interest in understanding and controlling the growth of bilayer graphene. Here we systematically investigate a broad set of flow rates and relative gas ratio of CH4 to H2 in atmospheric pressure chemical vapor deposition of multilayered graphene. Two very different growth windows are identified. For relatively high CH4 to H2 ratios, graphene growth is relatively rapid with an initial first full layer forming in seconds upon which new graphene flakes nucleate then grow on top of the first layer. The stacking of these flakes versus the initial graphene layer is mostly turbostratic. This growth mode can be likened to Stranski-Krastanov growth. With relatively low CH4 to H2 ratios, growth rates are reduced due to a lower carbon supply rate. In addition bi-, tri-, and few-layer flakes form directly over the Cu substrate as individual islands. Etching studies show that in this growth mode subsequent layers form beneath the first layer presumably through carbon radical intercalation. This growth mode is similar to that found with Volmer-Weber growth and was shown to produce highly oriented AB-stacked materials. These systematic studies provide new insight into bilayer graphene formation and define the synthetic range where gapped bilayer graphene can be reliably produced.

Sexithiophene Encapsulated in a Single-Walled Carbon Nanotube: An In Situ Raman Spectroelectrochemical Study of a Peapod Structure

The interaction of single-walled carbon nanotubes (SWCNTs) and α-sexithiophene (6T) was studied by Raman spectroscopy and by in situ Raman spectroelectrochemistry. The encapsulation of 6T in SWCNT and its interaction causes a bleaching of its photoluminescence, and also small shifts of its Raman bands. The Raman features of the SWCNT with embedded 6T (6T-peapods) change in both intensity and frequency compared to those of pristine SWCNT, which is a consequence of a change of the resonant condition. Electrochemical doping demonstrated that the electrode potential applied to the SWCNT wall causes changes in the embedded 6T. The effects of electrochemical charging on the Raman features of pristine SWCNT and 6T@SWCNT were compared. It is shown that the interaction of SWCNT with 6T also changes the electronic structure of SWCNT in its charged state. This change of electronic structure is demonstrated both for semiconducting and metallic tubes.

Retro-fitting an older (S)TEM with two Cs aberration correctors for 80 kV and 60 kV operation

For the characterization of light materials using transmission electron microscopy, a low electron acceleration voltage of 80 kV or even 60 kV is attractive due to reduced beam damage to the specimen. The concomitant reduction in resolving power of the microscope can be restored when using spherical aberration (Cs) correctors, which for the most part are only available in the latest and most expensive microscopes. Here, we show that upgrading of existing TEMs is an attractive and cost‐effective alternative. We report on the low‐voltage performance on graphitic material of a JEOL JEM‐2010F built in the early 1990s and retro‐fitted with a conventional imaging Cs corrector and a probe Cs corrector. The performance data show Cs retro‐fitted instruments can compete very favourably against more modern state‐of‐the‐art instruments in both conventional imaging (TEM) and scanning (STEM) modes.

Thermal Conductivity of Mechanically Joined Semiconducting/Metal Nanomembrane Superlattices

The decrease of thermal conductivity is crucial for the development of efficient thermal energy converters. Systems composed of a periodic set of very thin layers show among the smallest thermal conductivities reported to-date. Here, we fabricate in an unconventional but straightforward way hybrid superlattices consisting of a large number of nanomembranes mechanically stacked on top of each other. The superlattices can consist of an arbitrary composition of n- or p-type doped single-crystalline semiconductors and a polycrystalline metal layer. These hybrid multilayered systems are fabricated by taking advantage of the self-rolling technique. First, differentially strained nanomembranes are rolled into three-dimensional microtubes with multiple windings. By applying vertical pressure, the tubes are then compressed and converted into a planar hybrid superlattice. The thermal measurements show a substantial reduction of the cross-sectional heat transport through the nanomembrane superlattice compared to a single nanomembrane layer. Time-domain thermoreflectance measurements yield thermal conductivity values below 2 W m(-1) K(-1). Compared to bulk values, this represents a reduction of 2 orders of magnitude by the incorporation of the mechanically joined interfaces. The scanning thermal atomic force microscopy measurements support the observation of reduced thermal transport on top of the superlattices. In addition, small defects with a spatial resolution of ∼100 nm can be resolved in the thermal maps. The low thermal conductivity reveals the potential of this approach to fabricate miniaturized on-chip solutions for energy harvesters in, e.g., microautonomous systems.

Room temperature in situ growth of B/BOx nanowires and BOx nanotubes.

Despite significant advances in the synthesis of nanostructures, our understanding of the growth mechanisms of nanowires and nanotubes grown from catalyst particles remains limited. In this study we demonstrate a straightforward route to grow coaxial amorphous B/BOx nanowires and BOx nanotubes using gold catalyst particles inside a transmission electron microscope at room temperature without the need of any specialized or expensive accessories. Exceedingly high growth rates (over 7 μm/min) are found for the coaxial nanowires, and this is attributed to the highly efficient diffusion of B species along the surface of a nanowire by electrostatic repulsion. On the other hand the O species are shown to be relevant to activate the gold catalysts, and this can occur through volatile O species. The technique could be further developed to study the growth of other nanostructures and holds promise for the room temperature growth of nanostructures as a whole.

In situ observations of Pt nanoparticles coalescing inside carbon nanotubes

In this in situ study, details of the coalescence of Pt nanoparticles encapsulated within carbon nanotubes are investigated whilst under electron irradiation in aberration corrected transmission electron microscopy. Coalescence occurs via the direct attachment of atoms on the surface, particle reorientation and relaxation.