In Situ Transmission Electron Microscopy Modulation of Transport in Graphene Nanoribbons.

In situ transmission electron microscopy (TEM) electronic transport measurements in nanoscale systems have been previously confined to two-electrode configurations. Here, we use the focused electron beam of a TEM to fabricate a three-electrode geometry from a continuous 2D material where the third electrode operates as side gate in a field-effect transistor configuration. Specifically, we demonstrate TEM nanosculpting of freestanding graphene sheets into graphene nanoribbons (GNRs) with proximal graphene side gates, together with in situ TEM transport measurements of the resulting GNRs, whose conductance is modulated by the side-gate potential. The TEM electron beam displaces carbon atoms from the graphene sheet, and its position is controlled with nanometer precision, allowing the fabrication of GNRs of desired width immediately prior to each transport measurement. We also model the corresponding electric field profile in this three-terminal geometry. The implementation of an in situ TEM three-terminal platform shown here further extends the use of a TEM for device characterization. This approach can be easily generalized for the investigation of other nanoscale systems (2D materials, nanowires, and single molecules) requiring the correlation of transport and atomic structure.

Raman Shifts in Electron-Irradiated Monolayer MoS2.

We report how the presence of electron-beam-induced sulfur vacancies affects first-order Raman modes and correlate the effects with the evolution of the in situ transmission-electron microscopy two-terminal conductivity of monolayer MoS2 under electron irradiation. We observe a red-shift in the E' Raman peak and a less pronounced blue-shift in the A'1 peak with increasing electron dose. Using energy-dispersive X-ray spectroscopy and selected-area electron diffraction, we show that irradiation causes partial removal of sulfur and correlate the dependence of the Raman peak shifts with S vacancy density (a few %). This allows us to quantitatively correlate the frequency shifts with vacancy concentration, as rationalized by first-principles density functional theory calculations. In situ device current measurements show an exponential decrease in channel current upon irradiation. Our analysis demonstrates that the observed frequency shifts are intrinsic properties of the defective systems and that Raman spectroscopy can be used as a quantitative diagnostic tool to characterize MoS2-based transport channels.

Cross-Talk Between Ionic and Nanoribbon Current Signals in Graphene Nanoribbon-Nanopore Sensors for Single-Molecule Detection.

Nanopores are now being used not only as an ionic current sensor but also as a means to localize molecules near alternative sensors with higher sensitivity and/or selectivity. One example is a solid-state nanopore embedded in a graphene nanoribbon (GNR) transistor. Such a device possesses the high conductivity needed for higher bandwidth measurements and, because of its single-atomic-layer thickness, can improve the spatial resolution of the measurement. Here measurements of ionic current through the nanopore are shown during double-stranded DNA (dsDNA) translocation, along with the simultaneous response of the neighboring GNR due to changes in the surrounding electric potential. Cross-talk originating from capacitive coupling between the two measurement channels is observed, resulting in a transient response in the GNR during DNA translocation; however, a modulation in device conductivity is not observed via an electric-field-effect response during DNA translocation. A field-effect response would scale with GNR source-drain voltage (Vds), whereas the capacitive coupling does not scale with Vds . In order to take advantage of the high bandwidth potential of such sensors, the field-effect response must be enhanced. Potential field calculations are presented to outline a phase diagram for detection within the device parameter space, charting a roadmap for future optimization of such devices.

DNA Translocation in Nanometer Thick Silicon Nanopores.

Solid-state nanopores are single-molecule sensors that detect changes in ionic conductance (ΔG) when individual molecules pass through them. Producing high signal-to-noise ratio for the measurement of molecular structure in applications such as DNA sequencing requires low noise and large ΔG. The latter is achieved by reducing the nanopore diameter and membrane thickness. While the minimum diameter is limited by the molecule size, the membrane thickness is constrained by material properties. We use molecular dynamics simulations to determine the theoretical thickness limit of amorphous Si membranes to be ∼1 nm, and we designed an electron-irradiation-based thinning method to reach that limit and drill nanopores in the thinned regions. Double-stranded DNA translocations through these nanopores (down to 1.4 nm in thickness and 2.5 nm in diameter) provide the intrinsic ionic conductance detection limit in Si-based nanopores. In this regime, where the access resistance is comparable to the nanopore resistance, we observe the appearance of two conductance levels during molecule translocation. Considering the overall performance of Si-based nanopores, our work highlights their potential as a leading material for sequencing applications.

Electronic transport in heterostructures of chemical vapor deposited graphene and hexagonal boron nitride.

CVD graphene devices on stacked CVD hexagonal boron nitride (hBN) are demonstrated using a novel low-contamination transfer method, and their electrical performance is systematically compared to devices on SiO(2). An order of magnitude improvement in mobility, sheet resistivity, current density, and sustained power is reported when the oxide substrate is covered with five-layer CVD hBN.

Correlating atomic structure and transport in suspended graphene nanoribbons.

Graphene nanoribbons (GNRs) are promising candidates for next generation integrated circuit (IC) components; this fact motivates exploration of the relationship between crystallographic structure and transport of graphene patterned at IC-relevant length scales (<10 nm). We report on the controlled fabrication of pristine, freestanding GNRs with widths as small as 0.7 nm, paired with simultaneous lattice-resolution imaging and electrical transport characterization, all conducted within an aberration-corrected transmission electron microscope. Few-layer GNRs very frequently formed bonded-bilayers and were remarkably robust, sustaining currents in excess of 1.5 µA per carbon bond across a 5 atom-wide ribbon. We found that the intrinsic conductance of a sub-10 nm bonded bilayer GNR scaled with width as GBL(w) ≈ 3/4(e(2)/h)w, where w is the width in nanometers, while a monolayer GNR was roughly five times less conductive. Nanosculpted, crystalline monolayer GNRs exhibited armchair-terminated edges after current annealing, presenting a pathway for the controlled fabrication of semiconducting GNRs with known edge geometry. Finally, we report on simulations of quantum transport in GNRs that are in qualitative agreement with the observations.

Toward sensitive graphene nanoribbon-nanopore devices by preventing electron beam-induced damage.

Graphene-based nanopore devices are promising candidates for next-generation DNA sequencing. Here we fabricated graphene nanoribbon-nanopore (GNR-NP) sensors for DNA detection. Nanopores with diameters in the range 2-10 nm were formed at the edge or in the center of graphene nanoribbons (GNRs), with widths between 20 and 250 nm and lengths of 600 nm, on 40 nm thick silicon nitride (SiN(x)) membranes. GNR conductance was monitored in situ during electron irradiation-induced nanopore formation inside a transmission electron microscope (TEM) operating at 200 kV. We show that GNR resistance increases linearly with electron dose and that GNR conductance and mobility decrease by a factor of 10 or more when GNRs are imaged at relatively high magnification with a broad beam prior to making a nanopore. By operating the TEM in scanning TEM (STEM) mode, in which the position of the converged electron beam can be controlled with high spatial precision via automated feedback, we were able to prevent electron beam-induced damage and make nanopores in highly conducting GNR sensors. This method minimizes the exposure of the GNRs to the beam before and during nanopore formation. The resulting GNRs with unchanged resistances after nanopore formation can sustain microampere currents at low voltages (∼50 mV) in buffered electrolyte solution and exhibit high sensitivity, with a large relative change of resistance upon changes of gate voltage, similar to pristine GNRs without nanopores.

Continuous growth of hexagonal graphene and boron nitride in-plane heterostructures by atmospheric pressure chemical vapor deposition.

Graphene-boron nitride monolayer heterostructures contain adjacent electrically active and insulating regions in a continuous, single-atom thick layer. To date structures were grown at low pressure, resulting in irregular shapes and edge direction, so studies of the graphene-boron nitride interface were restricted to the microscopy of nanodomains. Here we report templated growth of single crystalline hexagonal boron nitride directly from the oriented edge of hexagonal graphene flakes by atmospheric pressure chemical vapor deposition, and physical property measurements that inform the design of in-plane hybrid electronics. Ribbons of boron nitride monolayer were grown from the edge of a graphene template and inherited its crystallographic orientation. The relative sharpness of the interface was tuned through control of growth conditions. Frequent tearing at the graphene-boron nitride interface was observed, so density functional theory was used to determine that the nitrogen-terminated interface was prone to instability during cool down. The electronic functionality of monolayer heterostructures was demonstrated through fabrication of field effect transistors with boron nitride as an in-plane gate dielectric.

In situ growth of cellular two-dimensional silicon oxide on metal substrates.

Crystalline hexagonally ordered silicon oxide layers with a thickness of less than a nanometer are grown on transition metal surfaces in an in situ electron microscopy experiment. The nucleation and growth of silica bilayers and monolayers, which represent the thinnest possible ordered structures of silicon oxide, are monitored in real time. The emerging layers show structural defects reminiscent of those in graphene and can also be vitreous. First-principles calculations provide atomistic insight into the energetics of the growth process. The interplay between the gain in silica-metal interaction energy due to their epitaxial match and energy loss associated with the mechanical strain of the silica network is addressed. The results of calculations indicate that both ordered and vitreous mono/bilayer structures are possible, so that the actual morphology of the layer is defined by the kinetics of the growth process.

Differentiation of short, single-stranded DNA homopolymers in solid-state nanopores.

In the last two decades, new techniques that monitor ionic current modulations as single molecules pass through a nanoscale pore have enabled numerous single-molecule studies. While biological nanopores have recently shown the ability to resolve single nucleotides within individual DNA molecules, similar developments with solid-state nanopores have lagged, due to challenges both in fabricating stable nanopores of similar dimensions as biological nanopores and in achieving sufficiently low-noise and high-bandwidth recordings. Here we show that small silicon nitride nanopores (0.8- to 2-nm diameter in 5- to 8-nm-thick membranes) can resolve differences between ionic current signals produced by short (30 base) ssDNA homopolymers (poly(dA), poly(dC), poly(dT)), when combined with measurement electronics that allow a signal-to-noise ratio of better than 10 to be achieved at 1-MHz bandwidth. While identifying intramolecular DNA sequences with silicon nitride nanopores will require further improvements in nanopore sensitivity and noise levels, homopolymer differentiation represents an important milestone in the development of solid-state nanopores.

Functionalized single-walled carbon nanotubes containing traces of iron as new negative MRI contrast agents for in vivo imaging.

Single-walled carbon nanotubes (SWCNTs) containing traces of iron oxide were functionalized by noncovalent lipid-PEG or covalent carboxylic acid function to supply new efficient MRI contrast agents for in vitro and in vivo applications. Longitudinal (r(1)) and transversal (r(2)) water proton relaxivities were measured at 300 MHz, showing a stronger T(2) feature as an MRI contrast agent (r(2)/r(1) = 190 for CO(2) H functionalisation). The r(2) relaxivity was demonstrated to be correlated to the presence of iron oxide in the SWNT-carboxylic function COOH, in comparison to iron-free ones. Biodistribution studies on mice after a systemic injection showed a negative MRI contrast in liver, suggesting the presence of the nanotubes in this organ until 48 h after i.v. injection. The presence of carbon nanotubes in liver was confirmed after ex vivo carbon extraction. Finally, cytotoxicity studies showed no apparent effect owing to the presence of the carbon nanotubes. The functionalized carbon nanotubes were well tolerated by the animals at the dose of 10 µg g(-1) body weight.

Engineering the atomic structure of carbon nanotubes by a focused electron beam: new morphologies at the sub-nanometer scale.

Carbon atoms are displaced in pre-selected locations of carbon nanotubes by using a focused electron beam in a scanning transmission electron microscope. Sub-nanometer-sized holes are created that change the morphology of double and triple-walled carbon nanotubes and connect the shells in a unique way. By combining in situ transmission electron microscopy experiments with atomistic simulations, we study the bonding between defective shells in the new structures which are reminiscent of the shape of a flute. We demonstrate that in double-walled nanotubes the shells locally merge by forming nanoarches while atoms with dangling bonds can be preserved in triple-walled carbon nanotubes. In the latter system, nanoarches are formed between the inner- and outermost shells, shielding small graphenic islands with open edges between the neighboring shells. Our results indicate that arrays of quantum dots may be produced in carbon nanotubes by spatially localized electron irradiation, generating atoms with dangling bonds that may give rise to localized magnetic moments.

Graphene growth by a metal-catalyzed solid-state transformation of amorphous carbon.

Single and few-layer graphene is grown by a solid-state transformation of amorphous carbon on a catalytically active metal. The process is carried out and monitored in situ in an electron microscope. It is observed that an amorphous carbon film is taken up by Fe, Co, or Ni crystals at temperatures above 600 °C. The nucleation and growth of graphene layers on the metal surfaces happen after the amorphous carbon film has been dissolved. It is shown that the transformation of the energetically less favorable amorphous carbon to the more favorable phase of graphene occurs by diffusion of carbon atoms through the catalytically active metal.

Defect-induced junctions between single- or double-wall carbon nanotubes and metal crystals.

Interfaces between the ends of single- or double-wall carbon nanotubes and metal crystals (Fe, Co, Pd, and Pt) are established by electron irradiation with nanometre precision at metal-nanotube contact areas. Calculations of the bonding energies at the metal-nanotube interfaces confirm that the formation of these covalent junctions is energetically favourable in the presence of a certain concentration of structural defects in the nanotubes. The process may be endothermic or exothermic in comparison with the unconnected configuration, but in either case atomic defects in carbon nanotubes are a necessary condition for joining them with metals.

Trapping of metal atoms in vacancies of carbon nanotubes and graphene.

Lattice defects in carbon nanotubes and graphene are created by focusing an electron beam in a scanning transmission electron microscope onto a 0.1 nm spot on the objects. Metal atoms migrating on the graphenic surfaces are observed to be trapped by these defects. Depending on the size of the defect, single metal atoms or clusters of several atoms can be localized in or on nanotubes or graphene layers. Subsequent escape of the metal atoms from the trapping centers gives information about the bonding between the metal atom and the defect. The process of trapping and detrapping is studied in a temperature range of 20-670 degrees C. The technique allows one to place metal atoms with almost atomic precision in graphenic structures and to create a predefined pattern of foreign atoms in graphene or carbon nanotubes.

Migration and localization of metal atoms on strained graphene.

Reconstructed point defects in graphene are created by electron irradiation and annealing. By applying electron microscopy and density functional theory, it is shown that the strain field around these defects reaches far into the unperturbed hexagonal network and that metal atoms have a high affinity to the nonperfect and strained regions of graphene. Metal atoms are attracted by reconstructed defects and bonded with energies of about 2 eV. The increased reactivity of the distorted π-electron system in strained graphene allows us to attach metal atoms and to tailor the properties of graphene.

Growth of single-walled carbon nanotubes from sharp metal tips.

The nucleation and growth of single-walled carbon nanotubes is observed in situ in a transmission electron microscope. Carbon atoms are implanted into catalytically active metal particles by electron-beam sputtering. The metal particles are then shaped with a focused electron beam. Once the particles have a region of high surface curvature, spontaneous nucleation and growth of single-walled carbon nanotubes occurs on the metal particles. It is shown that the local solubility of carbon in the metal determines the nucleation of nanotubes. This is confirmed by atomistic computer simulations treating the solubility of carbon in a metal particle as a function of the size of the system.

Cobalt nanoparticle-assisted engineering of multiwall carbon nanotubes.

New methods of processing multiwall carbon nanotubes (CNTs) are demonstrated in experiments in the transmission electron microscope (TEM). These include precisely controllable cutting, repairing, and interconnecting of different CNTs with the assistance of an encapsulated Co particle. All processes involve the interactions between the metal and graphitic shells that are driven by combined electrical biasing [using a scanning-tunneling microscope (STM)-TEM setup] of the CNT and focused electron-beam irradiation of a Co-containing region. In particular, we present two CNT soldering processes, that is, Co-joined and Co-catalytic connections. The former process uses a Co particle as the central node to which two CNTs are covalently attached on the opposite sides, and the latter makes use of the segregation of new graphitic shells from the metal at the connecting site, resulting in CNT plumbing. We compare the mechanical robustness of both connection types by direct force measurements in the TEM using an integrated atomic force microscope (AFM) setup. They reveal a tensile strength of 4.2 and 31 GPa, respectively, thus demonstrating the superiority of the Co-catalytic connection whose strength is already comparable to standard CNTs. In addition, all connected nanotubes show metallic conduction. The developed methods could be of particular importance in future nanoelectronic device technology.

Creation of individual vacancies in carbon nanotubes by using an electron beam of 1 A diameter.

The focused electron beam of an aberration-corrected scanning transmission electron microscope is used to create individual vacancies in predefined positions of carbon nanotubes. Vacancies in single-wall tubes are unstable and cause an immediate reconstruction of the lattice between 20 and 700 degrees C. In double-wall tubes, vacancies are stable and observable up to at least 235 degrees C, whereas above 480 degrees C a relaxation of the lattice occurs.

Heterojunctions between metals and carbon nanotubes as ultimate nanocontacts.

We report the controlled formation and characterization of heterojunctions between carbon nanotubes and different metal nanocrystals (Fe, Co, Ni, and FeCo). The heterojunctions are formed from metal-filled multiwall carbon nanotubes (MWNTs) via intense electron beam irradiation at temperatures in the range of 450-700 degrees C and observed in situ in a transmission electron microscope. Under irradiation, the segregation of metal and carbon atoms occurs, leading to the formation of heterojunctions between metal and graphite. Metallic conductivity of the metal-nanotube junctions was found by using in situ transport measurements in an electron microscope. Density functional calculations show that these structures are mechanically strong, the bonding at the interface is covalent, and the electronic states at and around the Fermi level are delocalized across the entire system. These properties are essential for the application of such heterojunctions as contacts in electronic devices and vital for the fabrication of robust nanotube-metal composite materials.