Graphene-Encapsulated Silver Nanoparticles for Plasmonic Vapor Sensing.

Graphene-covered silver nanoparticles were prepared directly on highly oriented pyrolytic graphite substrates and characterized by atomic force microscopy. UV-Vis reflectance spectroscopy was used to measure the shift in the local surface plasmon resonance (LSPR) upon exposure to acetone, ethanol, 2-propanol, toluene, and water vapor. The optical responses were found to be substance-specific, as also demonstrated by principal component analysis. Point defects were introduced in the structure of the graphene overlayer by O2 plasma. The LSPR was affected by the plasma treatment, but it was completely recovered using subsequent annealing. It was found that the presence of defects increased the response for toluene and water while decreasing it for acetone.

Special Issue: Synthesis and Characterization of Graphene-Based Hybrid Nanostructures.

Graphene has numerous outstanding physical properties such as excellent electron mobility, extremely high thermal conductivity, high flexibility, remarkable mechanical strength, and high transparency [...].

Synthesis and Characterization of Graphene-Silver Nanoparticle Hybrid Materials.

Silver nanoparticles (Ag NPs) play important roles in the development of plasmonic applications. Combining these nanoparticles with graphene can yield hybrid materials with enhanced light-matter interaction. Here, we report a simple method for the synthesis of graphene-silver nanoparticle hybrids on highly oriented pyrolytic graphite (HOPG) substrates. We demonstrate by scanning tunneling microscopy and local tunneling spectroscopy measurements the electrostatic n-type doping of graphene by contact with silver. We show by UV-Vis reflectance investigations that the local surface plasmon resonance (LSPR) of Ag NPs partially covered with graphene is preserved for at least three months, i.e., three times longer than the LSPR of bare Ag NPs. The gradual loss of LSPR is due to the spontaneous sulfurization of non-covered Ag NPs, as revealed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. We show that the Ag NPs completely sandwiched between graphene and HOPG do not sulfurize, even after one year.

Vapour sensing properties of graphene-covered gold nanoparticles.

We investigated the vapour sensing properties of different graphene-gold hybrid nanostructures. We observed the shifts in the optical spectra near the local surface plasmon resonance of the gold nanoparticles by changing the concentration and nature of the analytes (ethanol, 2-propanol, and toluene). The smaller, dome-like gold nanoparticles proved to be more sensitive to these vapours compared to slightly larger, flat nanoparticles. We investigated how the optical response of the gold nanoparticles can be tuned with a corrugated graphene overlayer. We showed that the presence of graphene increased the sensitivity to ethanol and 2-propanol, while it decreased it towards toluene exposure (at concentrations ≥ 30%). The slope changes observed on the optical response curves were discussed in the framework of capillary condensation. These results can have potential impact on the development of new sensors based on graphene-gold hybrids.

Dynamic strain in gold nanoparticle supported graphene induced by focused laser irradiation.

Graphene on noble-metal nanostructures constitutes an attractive nanocomposite with possible applications in sensors or energy conversion. In this work we study the properties of hybrid graphene/gold nanoparticle structures by Raman spectroscopy and scanning probe methods. The nanoparticles (NPs) were prepared by local annealing of gold thin films using a focused laser beam. The method resulted in a patterned surface, with NPs formed at arbitrarily chosen microscale areas. Graphene grown by chemical vapour deposition was transferred onto the prepared, closely spaced gold NPs. While we found that successive higher intensity (6 mW) laser irradiation increased gradually the doping and the defect concentration in SiO2 supported graphene, the same irradiation procedure did not induce such irreversible effects in the graphene supported by gold NPs. Moreover, the laser irradiation induced a dynamic hydrostatic strain in the graphene on Au NPs, which turned out to be completely reversible. These results can have implications in the development of graphene/plasmonic nanoparticle based high temperature sensors operating in dynamic regimes.

Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons.

The possibility that non-magnetic materials such as carbon could exhibit a novel type of s-p electron magnetism has attracted much attention over the years, not least because such magnetic order is predicted to be stable at high temperatures. It has been demonstrated that atomic-scale structural defects of graphene can host unpaired spins, but it remains unclear under what conditions long-range magnetic order can emerge from such defect-bound magnetic moments. Here we propose that, in contrast to random defect distributions, atomic-scale engineering of graphene edges with specific crystallographic orientation--comprising edge atoms from only one sub-lattice of the bipartite graphene lattice--can give rise to a robust magnetic order. We use a nanofabrication technique based on scanning tunnelling microscopy to define graphene nanoribbons with nanometre precision and well-defined crystallographic edge orientations. Although so-called 'armchair' ribbons display quantum confinement gaps, ribbons with the 'zigzag' edge structure that are narrower than 7 nanometres exhibit an electronic bandgap of about 0.2-0.3 electronvolts, which can be identified as a signature of interaction-induced spin ordering along their edges. Moreover, upon increasing the ribbon width, a semiconductor-to-metal transition is revealed, indicating the switching of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferromagnetic configuration. We found that the magnetic order on graphene edges of controlled zigzag orientation can be stable even at room temperature, raising hopes of graphene-based spintronic devices operating under ambient conditions.

Electric field-controlled rippling of graphene.

Metal-graphene interfaces generated by electrode deposition induce barriers or potential modulations influencing the electronic transport properties of graphene based devices. However, their impact on the local mechanical properties of graphene is much less studied. Here we show that graphene near a metallic interface can exhibit a set of ripples self-organized into domains whose topographic roughness is controlled by the tip bias of a scanning tunneling microscope. The reconstruction from topographic images of graphene bending energy maps sheds light on the local electro-mechanical response of graphene under STM imaging and unveils the role of the stress induced by the vicinity of the graphene-metal interface in the formation and the manipulation of these ripples. Since microscopic rippling is one of the important factors that limit charge carrier mobility in graphene, the control of rippling with a gate voltage may have important consequences in the conductance of graphene devices where transverse electric fields are created by contactless suspended gate electrodes. This opens up also the possibility to dynamically control the local morphology of graphene nanomembranes.