S. D. Barber

Self-organized platinum nanoparticles on freestanding graphene.

Freestanding graphene membranes were successfully functionalized with platinum nanoparticles (Pt NPs). High-resolution transmission electron microscopy revealed a homogeneous distribution of single-crystal Pt NPs that tend to exhibit a preferred orientation. Unexpectedly, the NPs were also found to be partially exposed to the vacuum with the top Pt surface raised above the graphene substrate, as deduced from atomic-scale scanning tunneling microscopy images and detailed molecular dynamics simulations. Local strain accumulation during the growth process is thought to be the origin of the NP self-organization. These findings are expected to shape future approaches in developing Pt NP catalysts for fuel cells as well as NP-functionalized graphene-based high-performance electronics.

Unusual ultra-low-frequency fluctuations in freestanding graphene

Intrinsic ripples in freestanding graphene have been exceedingly difficult to study. Individual ripple geometry was recently imaged using scanning tunnelling microscopy, but these measurements are limited to static configurations. Thermally-activated flexural phonon modes should generate dynamic changes in curvature. Here we show how to track the vertical movement of a one-square-angstrom region of freestanding graphene using scanning tunnelling microscopy, thereby allowing measurement of the out-of-plane time trajectory and fluctuations over long time periods. We also present a model from elasticity theory to explain the very-low-frequency oscillations. Unexpectedly, we sometimes detect a sudden colossal jump, which we interpret as due to mirror buckling. This innovative technique provides a much needed atomic-scale probe for the time-dependent behaviours of intrinsic ripples. The discovery of this novel progenitor represents a fundamental advance in the use of scanning tunnelling microscopy, which together with the application of a thermal load provides a low-frequency nano-resonator.

Electronic transition from graphite to graphene via controlled movement of the top layer with scanning tunneling microscopy

A series of measurements using a technique called electrostatic-manipulation scanning tunneling microscopy (EM-STM) were performed on a highly oriented pyrolytic graphite surface. The electrostatic interaction between the STM tip and the sample can be tuned to produce both reversible and irreversible large-scale movement of the graphite surface. Under this influence, atomic-resolution STM images reveal that a continuous electronic transition from triangular symmetry, where only alternate atoms are imaged, to hexagonal symmetry can be systematically controlled. Density functional theory (DFT) calculations reveal that this transition can be related to vertical displacements of the top layer of graphite relative to the bulk. Evidence for horizontal shifts in the top layer of graphite is also presented. Excellent agreement is found between experimental STM images and those simulated using DFT.

Thermal mirror buckling in freestanding graphene locally controlled by scanning tunnelling microscopy

Knowledge of and control over the curvature of ripples in freestanding graphene are desirable for fabricating and designing flexible electronic devices, and recent progress in these pursuits has been achieved using several advanced techniques such as scanning tunnelling microscopy. The electrostatic forces induced through a bias voltage (or gate voltage) were used to manipulate the interaction of freestanding graphene with a tip (substrate). Such forces can cause large movements and sudden changes in curvature through mirror buckling. Here we explore an alternative mechanism, thermal load, to control the curvature of graphene. We demonstrate thermal mirror buckling of graphene by scanning tunnelling microscopy and large-scale molecular dynamic simulations. The negative thermal expansion coefficient of graphene is an essential ingredient in explaining the observed effects. This new control mechanism represents a fundamental advance in understanding the influence of temperature gradients on the dynamics of freestanding graphene and future applications with electro-thermal-mechanical nanodevices.

A pathway between Bernal and rhombohedral stacked graphene layers with scanning tunneling microscopy

Horizontal shifts in the top layer of highly oriented pyrolytic graphite, induced by a scanning tunneling microscope (STM) tip, are presented. Excellent agreement is found between STM images and those simulated using density functional theory. First-principle calculations identify that the low-energy barrier direction of the top layer displacement is toward a structure where none of the carbon pz orbitals overlap, while the high-energy barrier direction is toward AA stacking. Each directional shift yields a real-space surface charge density similar to graphene; however, the low-energy barrier direction requires only one bond length to convert ABA (Bernal) to ABC (rhombohedral).

High-percentage success method for preparing and pre-evaluating tungsten tips for atomic-resolution scanning tunneling microscopy

A custom double-lamella method is presented for electrochemically etching tungsten wire for use as tips in scanning tunneling microscopy (STM). For comparison, tips were also manufactured in-house using numerous conventional methods and examined using an optical microscope. Both sets of tips were used to obtain STM images of highly oriented pyrolytic graphite, the quality of which varied. The clarity of the STM images was found to be correlated to the optically measured cone angle of the STM tip, with larger cone angles consistently producing atomically resolved images. The custom etching procedure described allows one to create larger cone angles and consequently proved superior in reliably producing high-quality tips.

Role of bias voltage and tunneling current in the perpendicular displacements of freestanding graphene via scanning tunneling microscopy

Systematic displacement measurements of freestanding graphene as a function of applied bias voltage and tunneling current setpoint using scanning tunneling microscopy (STM) are presented. When the bias voltage is increased the graphene approaches the STM tip, while, on the other hand, when the tunneling current is increased the graphene contracts from the STM tip. To understand the role of the bias voltage, we quantitatively model the attractive force between the tip and the sample using electrostatics. For the tunneling current, we qualitatively model the contraction of the graphene using entropic concepts. These complementary results enhance the understanding of each other and highlight peculiarities of the system.

Graphene Manipulation on 4H-SiC(0001) Using Scanning Tunneling Microscopy

Atomic-scale topography of epitaxial multilayer graphene grown on 4H-SiC(0001) was investigated using scanning tunneling microscopy (STM). Bunched nano-ridges ten times smaller than previously recorded were observed throughout the surface, the morphology of which was systematically altered using a relatively new technique called electrostatic-manipulation scanning tunneling microscopy. Transformed graphene formations sometimes spontaneously returned to their original morphology, while others permanently changed. Using an electrostatic model, we calculate that a force up to ~5 nN was exerted by the STM tip, and an energy of around 10 eV was required to alter the geometry of a ~100×200 nm2 area.

Atomic-scale movement induced in nanoridges by scanning tunneling microscopy on epitaxial graphene grown on 4H-SiC(0001)

Nanoscale ridges in epitaxial multilayer graphene grown on the silicon face of 4° off-cut 4H-SiC (0001) were found using scanning tunneling microscopy (STM). These nanoridges are only 0.1 nm high and 25–50 nm wide, making them much smaller than previously reported ridges. Atomic-resolution STM was performed near and on top of the nanoridges using a dual scanning technique in which forward and reverse images are simultaneously recorded. An apparent 100% enlarged graphene lattice constant is observed along the leading edge of the image for both directions. Horizontal movement of the graphene, due to both an electrostatic attraction to the STM tip and weak bonding to the substrate, is thought to contribute to the results.

Schottky barrier and attenuation length for hot hole injection in nonepitaxial Au on p-type GaAs

Ballistic electron emission microscopy (BEEM) was performed to obtain current versus bias characteristics of nonepitaxial nanometer-thick Au on p-type GaAs in order to accurately measure the local Schottky barrier height. Hole injection BEEM data were averaged from thousands of spectra for various Au film thicknesses and then used to determine the attenuation length of the energetic charge carriers as a function of tip bias. The authors report an increase in attenuation length at biases near the Schottky barrier, providing evidence for the existence of coherent BEEM currents in Schottky diodes. These results provide additional evidence for the conservation of the parallel momentum of charge carriers at the metal–semiconductor interface.