Highlighting the Dynamics of Graphene Protection toward the Oxidation of Copper Under Operando Conditions.

We performed spatially resolved near-ambient-pressure photoemission spectromicroscopy on graphene-coated copper in operando under oxidation conditions in an oxygen atmosphere (0.1 mbar). We investigated regions with bare copper and areas covered with mono- and bi-layer graphene flakes, in isobaric and isothermal experiments. The key method in this work is the combination of spatial and chemical resolution of the scanning photoemission microscope operating in a near-ambient-pressure environment, thus allowing us to overcome both the material and pressure gap typical of standard ultrahigh-vacuum X-ray photoelectron spectroscopy (XPS) and to observe in operando the protection mechanism of graphene toward copper oxidation. The ability to perform spatially resolved XPS and imaging at high pressure allows for the first time a unique characterization of the oxidation phenomenon by means of photoelectron spectromicroscopy, pushing the limits of this technique from fundamental studies to real materials under working conditions. Although bare Cu oxidizes naturally at room temperature, our results demonstrate that such a graphene coating acts as an effective barrier to prevent copper oxidation at high temperatures (over 300 °C), until oxygen intercalation beneath graphene starts from boundaries and defects. We also show that bilayer flakes can protect at even higher temperatures. The protected metallic substrate, therefore, does not suffer corrosion, preserving its metallic characteristic, making this coating appealing for any application in an aggressive atmospheric environment at high temperatures.

Chemically deposited palladium nanoparticles on graphene for hydrogen sensor applications.

Graphene decorated by palladium (Pd) nanoparticles has been investigated for hydrogen sensor applications. The density of Pd nanoparticles is critical for the sensor performance. We develop a new chemical method to deposit high-density, small-size and uniformly-distributed Pd nanoparticles on graphene. With this method, Pd precursors are connected to the graphene by π-π bonds without introducing additional defects in the hexagonal carbon lattice. Our method is simple, cheap, and compatible with complementary metal-oxide semiconductor (CMOS) technology. This method is used to fabricate hydrogen sensors on 3-inch silicon wafers. The sensors show high performance at room temperature. Particularly, the sensors present a shorter recovery time under light illumination. The sensing mechanism is explained and discussed. The proposed deposition method facilitates mass fabrication of the graphene sensors and allows integration with CMOS circuits for practical applications.

Restoring self-limited growth of single-layer graphene on copper foil via backside coating.

The growth of single-layer graphene (SLG) by chemical vapor deposition (CVD) on copper surfaces is very popular because of the self-limiting effect that, in principle, prevents the growth of few-layer graphene (FLG). However, the reproducibility of the CVD growth of homogeneous SLG remains a major challenge, especially if one wants to avoid heavy surface treatments, monocrystalline substrates and expensive equipment to control the atmosphere inside the growth system. We demonstrate here that backside tungsten coating of copper foils allows for the exclusive growth of SLG with full coverage by atmospheric pressure CVD implemented in a vacuum-free furnace. We show that the absence of FLG patches is related to the suppression of carbon diffusion through copper. In the perspective of large-scale production of graphene, this approach constitutes a significant improvement to the traditional CVD growth process since (1) a tight control of the hydrocarbon flow is no longer required to avoid FLG formation and, consequently, (2) the growth duration necessary to reach full coverage can be drastically shortened.

Toward the use of CVD-grown MoS2 nanosheets as field-emission source.

Densely populated edge-terminated vertically aligned two-dimensional MoS2 nanosheets (NSs) with thicknesses ranging from 5 to 20 nm were directly synthesized on Mo films deposited on SiO2 by sulfurization. The quality of the obtained NSs was analyzed by scanning electron and transmission electron microscopy, and Raman and X-ray photoelectron spectroscopy. The as-grown NSs were then successfully transferred to the substrates using a wet chemical etching method. The transferred NSs sample showed excellent field-emission properties. A low turn-on field of 3.1 V/µm at a current density of 10 µA/cm2 was measured. The low turn-on field is attributed to the morphology of the NSs exhibiting vertically aligned sheets of MoS2 with sharp and exposed edges. Our findings show that the fabricated MoS2 NSs could have a great potential as robust high-performance electron-emitter material for various applications such as microelectronics and nanoelectronics, flat-panel displays and electron-microscopy emitter tips.

Decorating graphene with size-selected few-atom clusters: a novel approach to investigate graphene-adparticle interactions.

We investigated the interaction between size-selected Au2 and Au3 clusters and graphene. Hereto preformed clusters are deposited on graphene field-effect transistors, a novel approach which offers a high control over the number of atoms per cluster, the deposition energy and the deposited density. The induced p-doping and charge carrier scattering indicate that a major part of the deposited clusters remains on the graphene flake as either individual or sub-nm coalesced entities. This is independently confirmed by scanning electron microscopy on the same devices after current annealing. Our novel approach provides perspectives for the electronic sensing of metallic clusters down to their atom-by-atom size-specific properties, and exploiting the tunability of clusters for tailoring desired properties in graphene.

Recurrent Quantum Scars in a Mesoscopic Graphene Ring.

When coherent charge carriers cross micron-scale cavities, their dynamics can be governed by a few resonant states, also called "quantum scars", determined by the cavity geometry. Quantum scars can be described using theoretical tools but have also been directly imaged in the case of high-quality semiconductor cavities as well as in disordered graphene devices, thanks to scanning gate microscopy (SGM). Here, we discuss spatially resolved SGM images of low-temperature charge transport through a mesoscopic ring fabricated from high-quality monolayer graphene lying on top of hexagonal boron nitride. SGM images are decorated with a pattern of radial scars in the ring area, which is found to evolve smoothly and reappear when varying the charge-carrier energy. The energies separating recurrent patterns are found to be directly related to geometric dimensions of the ring. Moreover, a recurrence is also observed in simulations of the local density of states of a model graphene quantum ring. The observed recurrences are discussed in the light of recent predictions of relativistic quantum scars in mesoscopic graphene cavities.

Oxidation-assisted graphene heteroepitaxy on copper foil.

We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.

Probing Graphene χ((2)) Using a Gold Photon Sieve.

Nonlinear second harmonic optical activity of graphene covering a gold photon sieve was determined for different polarizations. The photon sieve consists of a subwavelength gold nanohole array placed on glass. It combines the benefits of efficient light trapping and surface plasmon propagation to unravel different elements of graphene second-order susceptibility χ((2)). Those elements efficiently contribute to second harmonic generation. In fact, the graphene-coated photon sieve produces a second harmonic intensity at least two orders of magnitude higher compared with a bare, flat gold layer and an order of magnitude coming from the plasmonic effect of the photon sieve; the remaining enhancement arises from the graphene layer itself. The measured second harmonic generation yield, supplemented by semianalytical computations, provides an original method to constrain the graphene χ((2)) elements. The values obtained are |d31 + d33| ≤ 8.1 × 10(3) pm(2)/V and |d15| ≤ 1.4 × 10(6) pm(2)/V for a second harmonic signal at 780 nm. This original method can be applied to any kind of 2D materials covering such a plasmonic structure.

Damage evaluation in graphene underlying atomic layer deposition dielectrics.

Based on micro-Raman spectroscopy (µRS) and X-ray photoelectron spectroscopy (XPS), we study the structural damage incurred in monolayer (1L) and few-layer (FL) graphene subjected to atomic-layer deposition of HfO2 and Al2O3 upon different oxygen plasma power levels. We evaluate the damage level and the influence of the HfO2 thickness on graphene. The results indicate that in the case of Al2O3/graphene, whether 1L or FL graphene is strongly damaged under our process conditions. For the case of HfO2/graphene, µRS analysis clearly shows that FL graphene is less disordered than 1L graphene. In addition, the damage levels in FL graphene decrease with the number of layers. Moreover, the FL graphene damage is inversely proportional to the thickness of HfO2 film. Particularly, the bottom layer of twisted bilayer (t-2L) has the salient features of 1L graphene. Therefore, FL graphene allows for controlling/limiting the degree of defect during the PE-ALD HfO2 of dielectrics and could be a good starting material for building field effect transistors, sensors, touch screens and solar cells. Besides, the formation of Hf-C bonds may favor growing high-quality and uniform-coverage dielectric. HfO2 could be a suitable high-K gate dielectric with a scaling capability down to sub-5-nm for graphene-based transistors.

Robust electromagnetic absorption by graphene/polymer heterostructures.

Polymer/graphene heterostructures present good shielding efficiency against GHz electromagnetic perturbations. Theory and experiments demonstrate that there is an optimum number of graphene planes, separated by thin polymer spacers, leading to maximum absorption for millimeter waves Batrakov et al (2014 Sci. Rep. 4 7191). Here, electrodynamics of ideal polymer/graphene multilayered material is first approached with a well-adapted continued-fraction formalism. In a second stage, rigorous coupled wave analysis is used to account for the presence of defects in graphene that are typical of samples produced by chemical vapor deposition, namely microscopic holes, microscopic dots (embryos of a second layer) and grain boundaries. It is shown that the optimum absorbance of graphene/polymer multilayers does not weaken to the first order in defect concentration. This finding testifies to the robustness of the shielding efficiency of the proposed absorption device.

Gas sensing with gold-decorated vertically aligned carbon nanotubes.

Vertically aligned carbon nanotubes of different lengths (150, 300, 500 µm) synthesized by thermal chemical vapor deposition and decorated with gold nanoparticles were investigated as gas sensitive materials for detecting nitrogen dioxide (NO2) at room temperature. Gold nanoparticles of about 6 nm in diameter were sputtered on the top surface of the carbon nanotube forests to enhance the sensitivity to the pollutant gas. We showed that the sensing response to nitrogen dioxide depends on the nanotube length. The optimum was found to be 300 µm for getting the higher response. When the background humidity level was changed from dry to 50% relative humidity, an increase in the response to NO2 was observed for all the sensors, regardless of the nanotube length.

Self-formation of sub-10 nm nanogaps based on silicidation.

We have developed a simple and reliable method for the fabrication of sub-10 nm wide nanogaps. The self-formed nanogap is based on the stoichiometric solid-state reaction between metal and silicon atoms during the silicidation process. The nanogap width is determined by the metal layer thickness. Our proposed method can produce symmetric and asymmetric electrode nanogaps, as well as multiple nanogaps within one unique process step, for potential application to biological/chemical sensors and nanoelectronics, such as resistive switches, storage devices, and vacuum channel transistors. This method provides high throughput and it is suitable for large-scale production.

Energy-band engineering for improved charge retention in fully self-aligned double floating-gate single-electron memories.

We present a new fully self-aligned single-electron memory with a single pair of nano floating gates, made of different materials (Si and Ge). The energy barrier that prevents stored charge leakage is induced not only by quantum effects but also by the conduction-band offset that arises between Ge and Si. The dimensions and position of each floating gate are well-defined and controlled. The devices exhibit a long retention time and single-electron injection at room temperature.

Characterization of ultrathin SOI film and application to short channel MOSFETs.

In this study, a very dilute solution (NH(4)OH:H(2)O(2):H(2)O 1:8:64 mixture) was employed to reduce the thickness of commercially available SOI wafers down to 3 nm. The etch rate is precisely controlled at 0.11 Å s(-1) based on the self-limited etching speed of the solution. The thickness uniformity of the thin film, evaluated by spectroscopic ellipsometry and by high-resolution x-ray reflectivity, remains constant through the thinning process. Moreover, the film roughness, analyzed by atomic force microscopy, slightly improves during the thinning process. The residual stress in the thin film is much smaller than that obtained by sacrificial oxidation. Mobility, measured by means of a bridge-type Hall bar on 15 nm film, is not significantly reduced compared to the value of bulk silicon. Finally, the thinned SOI wafers were used to fabricate Schottky-barrier metal-oxide-semiconductor field-effect transistors with a gate length down to 30 nm, featuring state-of-the-art current drive performance.