Knock-on damage in bilayer graphene: Indications for a catalytic pathway

We study by high-resolution transmission electron microscopy the structural response of bilayer graphene to electron irradiation with energies below the knock-on damage threshold of graphene. We observe that one type of divacancy, which we refer to as the butterfly defect, is formed for radiation energies and doses for which no vacancies are formed in clean monolayer graphene. By using first principles calculations based on density-functional theory, we analyze two possible causes related with the presence of a second layer that could explain the observed phenomenon: an increase of the defect stability or a catalytic effect during its creation. For the former, the obtained formation energies of the defect in monolayer and bilayer systems show that the change in stability is negligible. For the latter, ab initio molecular dynamics simulations indicate that the threshold energy for direct expulsion does not decrease in bilayer graphene as compared with monolayer graphene, and we demonstrate the possibility of creating divacancies through catalyzed intermediate states below this threshold energy. The estimated cross section agrees with what is observed experimentally. Therefore, we show the possibility of a catalytic pathway for creating vacancies under electron radiation below the expulsion threshold energy. © 2013 American Physical Society

Stability of graphene doping with MoO<inf>3</inf>and I<inf>2</inf>

We dope graphene by evaporation of MoO_3 or by solution-deposition of I_2 and assess the doping stability for its use as transparent electrodes. Electrical measurements show that both dopants increase the graphene sheet conductivity and find that MoO_3-doped graphene is significantly more stable during thermal cycling. Raman spectroscopy finds that neither dopant creates defects in the graphene lattice. In-situ photoemission determines the minimum necessary thickness of MoO_3 for full graphene doping.This is the author's accepted manuscript. Copyright (2014) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters (volume 105) and may be found at http://scitation.aip.org/content/aip/journal/apl/105/10/10.1063/1.489502

Investigation of charges-driven interactions between graphene and different SiO2 surfaces

As being only one atom thick, most of the device applications require graphene to be partially or fully supported by a substrate, which is typically silicon dioxide (SiO2). According to a common understanding, graphene interacts with SiO2 through weak, long-range van der Waals forces, emerging between instantaneous/induced dipoles, in contrast to the experimental evidence that reveals a surprisingly high interaction between graphene and SiO2. In order to get further insight into this phenomenon, we carried out diverse physical measurements on SiO2 substrates, prepared via different fabrication protocols, with and without graphene on top. As a result, the role of the oxide surface charges is recognized for the first time as a main factor causing graphene to strongly interact with SiO2. Our findings provide guidelines for designing 2D materials interaction with a substrate through modulation of surface charges. This, in turn, can facilitate the development of new graphene based microelectronic devices

Ultra-low contact resistance in graphene devices at the Dirac point

Contact resistance is one of the main factors limiting performance of short-channel graphene field-effect transistors (GFETs), preventing their use in low-voltage applications. Here we investigated the contact resistance between graphene grown by chemical vapor deposition (CVD) and different metals, and found that etching holes in graphene below the contacts consistently reduced the contact resistance, down to 23 Omega . mu m with Au contacts. This low contact resistance was obtained at the Dirac point of graphene, in contrast to previous studies where the lowest contact resistance was obtained at the highest carrier density in graphene (here 200 Omega . mu m was obtained under such conditions). The 'holey' Au contacts were implemented in GFETs which exhibited an average transconductance of 940 S m(-1) at a drain bias of only 0.8 V and gate length of 500 nm, which out-perform GFETs with conventional Au contacts

Real-space mapping of tailored sheet and edge plasmons in graphene nanoresonators

Plasmons in graphene nanoresonators have many potential applications in photonics and optoelectronics, including room-temperature infrared and terahertz photodetectors, sensors, reflect arrays or modulators1, 2, 3, 4, 5, 6, 7. The development of efficient devices will critically depend on precise knowledge and control of the plasmonic modes. Here, we use near-field microscopy8, 9, 10, 11 between λ0 = 10–12 μm to excite and image plasmons in tailored disk and rectangular graphene nanoresonators, and observe a rich variety of coexisting Fabry–Perot modes. Disentangling them by a theoretical analysis allows the identification of sheet and edge plasmons, the latter exhibiting mode volumes as small as 10−8λ03. By measuring the dispersion of the edge plasmons we corroborate their superior confinement compared with sheet plasmons, which among others could be applied for efficient 1D coupling of quantum emitters12. Our understanding of graphene plasmon images is a key to unprecedented in-depth analysis and verification of plasmonic functionalities in future flatland technologies.Peer ReviewedPostprint (author's final draft

Correction to: The Role of Adsorbed and Subsurface Carbon Species for the Selective Alkyne Hydrogenation Over a Pd-Black Catalyst: An Operando Study of Bulk and Surface

The selective hydrogenation of propyne over a Pd-black model catalyst was investigated under operando conditions at 1 bar making use of advanced X-ray diffraction (bulk sensitive) and photo-electron spectroscopy (surface sensitive) techniques. It was found that the population of subsurface species controls the selective catalytic semi-hydrogenation of propyne to pro-pylene due to the formation of surface and near-surface PdCx that inhibits the participation of more reactive bulk hydrogen in the hydrogenation reaction. However, increasing the partial pressure of hydrogen reduces the population of PdCx with the concomitant formation of a β-PdHx phase up to the surface, which is accompanied by a lattice expansion, allowing the participation of more active bulk hydrogen which is responsible for the unselective total alkyne hydrogenation. Therefore, controlling the surface and subsurface catalyst chemistry is crucial to control the selective alkyne semi-hydrogenation

Surface Electron-Hole Rich Species Active in the Electrocatalytic Water Oxidation

Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and ab initio DFT calculations, we were able to reveal the electronic structure of the active IrOx centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally IrV species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (μ1-O and μ1-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (μ3-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a μ1-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species