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 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 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.
Ru nanoparticles (NPs) can precipitate in Ru doped SiO2 amorphous thin films, triggered by electron irradiation in (scanning) transmission electron microscope ((S)TEM). A new mechanism was introduced to interpret the formation of metal NPs in (S)TEM. The induced electric field by electron irradiation, which originates from charging due to ionizations and excitations of atom electrons, can reduce the Gibbs free energy barrier for nucleation of metal particles. Furthermore, the directional ion drifting driven by the electric forces may accelerate the kinetic process of metal particle precipitati…
The acceleration of an spheroidal metal nanoparticle in an irradiation field with a frequency close to the surface plasmon vibration has been considered. Under the action of radiation pressure, the polarizability for nonspherical particle becomes a tensor quantity. The analytical expressions for the resonance acceleration components for the cases of plane-polarized and circularly polarized light have been derived. We have demonstrated that the resonance acceleration can depend substantially on the shape of a metal nanoparticle and its orientation with respect to the directions of light propaga…
We form single-electron transistors from individual chemically-synthesized gold nanoparticles, 5-15 nm in diameter, with monolayers of organic molecules serving as tunnel barriers. These devices allow us to measure the discrete electronic energy levels of individual gold nanoparticles that are, by virtue of chemical synthesis, well-defined in their composition, size and shape. We show that the nanoparticles are non-magnetic and have spectra in good accord with random-matrix-theory predictions taking into account strong spin-orbit coupling.
The last two decades have witnessed various experiments reporting very unusual magnetic properties of ensembles of gold nanoparticles surrounded by organic ligands, including ferromagnetic, paramagnetic, or (large) diamagnetic responses. These behaviors are at odds with the small diamagnetic response of macroscopic gold samples. Here we theoretically investigate the possibility that the observed unusual magnetism in capped gold nanoparticles is of orbital origin. Employing semiclassical techniques, we calculate the orbital component to the zero-field susceptibility of individual as well as ens…
In this letter, we report a chemical route for synthesizing SiO2@Au core-shell nanoparticles. The process includes four steps: i) preparation of the silica cores, ii) grafting gold nanoparticles over SiO2 cores, iii) priming of the silica-coated gold nanoparticles with 2 and 10 nm gold colloids and finally iv) formation of complete shell. The optical extinction spectra were experimentally measured and compared to numerical calculations in order to confirm the dimensions deduced from SEM images. Finally, the potential of such core-shell nanoparticles for biosensing was probed by means of Surfac…
A simple and highly reproducible technique is demonstrated for the fabrication of metallic electrodes with nanometer separation. Commercially available bare gold colloidal nanoparticles are first trapped between prefabricated large-separation electrodes to form a low-resistance bridge by an ac electric field. A large dc voltage is then applied to break the bridge via electromigration at room temperature, which consistently produces gaps in the sub-10 nm range. The technique is readily applied to prefabricated electrodes with separation up to 1 micron, which can be defined using optical lithogr…
Electron beam imaging is a common technique used for characterizing the morphology of plasmonic nanostructures. During the imaging process, the electron beam interacts with traces of organic material in the chamber and produces a well-know layer of amorphous carbon over the specimen under investigation. In this paper, we investigate the effect of this carbon adsorbate on the spectral position of the surface plasmon in individual gold nanoparticles as a function of electron exposure dose. We find an optimum dose for which the plasmonic response of the nanoparticle is not affected by the imaging…
A novel approach to control the grain size of oxide thin film materials has been investigated. Perovskite BaTiO3 shows interesting grain structures when deposited on gold predeposited, (111)-oriented, singlecrystal SrTiO3 substrates. Solid oxide films grow epitaxially on patterned seed layers and show variations in grain size relative to the films deposited on SrTiO3 directly.
We present a theoretical model for describing light scattering from randomly distributed Au nanoparticles on a substrate, including the clustering effect. By using the finite-element Green function method and spherical harmonic basis functions, we are able to calculate the polarization-dependent reflectivity spectra of the system (modeled by randomly distributed nanoparticles coupled with clusters) efficiently and accurately. The calculated ellipsometric spectra of the system with clusters can adequately describe the experimental data for the whole frequency range. We find that the clustering …
We show that silver nanoparticles, which are deposited on a terahertz-receiving antenna, can be sintered by intense terahertz pulse irradiation. The conductance of the silver nanoparticles between the antenna electrodes is measured under the terahertz pulse irradiation. The dispersant materials surrounding the nanoparticles are peeled off, and conduction paths are created. We reveal that, during sintering, quantum point contacts are formed, leading to quantized conductance between the electrodes with the conductance quantum, which reflects the formation of atomically thin wires. The terahertz …
The influence of delay-time between two sequential femtosecond pulses on the properties of nanoparticles obtained via laser ablation of gold in ethanol has been studied. The morphological and optical properties of the nanoparticles attained were characterized using high resolution transmission electron microscopy and UV_Vis absorption spectroscopy, respectively. Furthermore, the size distribution of nanoparticles was determined by means of a centrifugal sedimentation particle size analyzer. It is found that the time delay variations lead to corresponding changes in size distribution, plasmon r…
Atomically thin boron nitride (BN) nanosheets have many properties desirable for surface enhanced Raman spectroscopy (SERS). BN nanosheets have a strong surface adsorption capability towards airborne hydrocarbon and aromatic molecules. For maximized adsorption area and hence SERS sensitivity, atomically thin BN nanosheet covered gold nanoparticles have been prepared for the first time. When placed on top of metal nanoparticles, atomically thin BN nanosheets closely follow their contours so that the plasmonic hot spots are retained. Electrically insulating BN nanosheets also act as a barrier la…
Optical nanoantennas are a novel tool to investigate previously unattainable dimensions in the nanocosmos. Just like their radio-frequency equivalents, nanoantennas enhance the light-matter interaction in their feed gap. Antenna enhancement of small signals promises to open a new regime in linear and nonlinear spectroscopy on the nanoscale. Without antennas especially the nonlinear spectroscopy of single nanoobjects is very demanding. Here, we present for the first time antenna-enhanced ultrafast nonlinear optical spectroscopy. In particular, we utilize the antenna to determine the nonlinear t…
Specialized applications of nanoparticles often call for particular, well-characterized particle size distributions in solution. But, this property can prove difficult to measure. High-throughput methods, such as dynamic light scattering, detect nanoparticles in solution with an efficiency that scales with diameter to the sixth power. This diminishes the accuracy of any determination that must span a range of particle sizes. The accurate classification of broadly distributed systems thus requires very large numbers of measurements. Mass-filtered particle-sensing techniques offer a better dynam…
Applying ac voltages, we trapped gold nanoparticles between microfabricated electrodes under well-defined conditions. We demonstrate that the nanoparticles can be controllably fused together to form homogeneous gold nanowires with pre-defined diameters and conductance values. Whereas electromigration is known to form a gap when a dc voltage is applied, this ac technique achieves the opposite, thereby completing the toolkit for the fabrication of nanoscale junctions.
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 incr…
Origin of the rich polymorphism of gold in penta-twinned nanoparticles
Université de Genève（日内瓦大学）；University of Cantabria（坎塔布里亚大学）；Centro de Física de Materiales (CSIC-UPV/EHU)（材料物理中心（西班牙科学研究中心-巴斯克国立大学））；Synchrotron SOLEIL（SOLEIL同步辐射中心）；CIC biomaGUNE（CIC生物医学研究中心）；Ikerbasque, Basque Foundation for Science（伊克拉巴斯科，巴斯克科学基金会）
Graphene covered metal nanoparticles constitute a novel type of hybrid materials, which provide a unique platform to study plasmonic effects, surface-enhanced Raman scattering (SERS), and metal-graphene interactions at the nanoscale. Such a hybrid material is fabricated by transferring graphene grown by chemical vapor deposition onto closely spaced gold nanoparticles produced on a silica wafer. The morphology and physical properties of nanoparticle-supported graphene is investigated by atomic force microscopy, optical reflectance spectroscopy, scanning tunneling microscopy and spectroscopy (ST…
The radiative heat transfer between gold nanoparticle layers is presented using the coupled dipole method. Gold nanoparticles are modelled as effective electric and magnetic dipoles interacting via electromagnetic fluctuations. The effect of higher-order multipoles is implemented in the expression of electric polarizability to calculate the interactions at short distances. Our findings show that the near-field radiation reduces as the radius of the nanoparticles is increased. Also, the magnetic dipole contribution to the heat exchange becomes more important for larger particles. When one layer…
Bulk gold is a good metal, i.e., conductor of electricity and heat, due to its delocalized electron density that can respond to extremely small external perturbations such as electric field or temperature gradient. In energy space, the quantum states of the conduction electrons cross over the metal's Fermi energy continuously. But when gold is dispersed in finite nanometer-size particles or 'clusters', the delocalized electronic states are re-grouped in energy space to 'shells' according to allowed energy levels and the symmetry and shape of the atomic arrangement. This re-grouping generates a…
We present here an original process combining top-down and bottom-up approaches by annealing a thin gold film evaporated onto a hole template made by etching a PS-PMMA copolymer film. Such process allows a better control of the gold nanoparticle size distribution which provides a sharper localized surface plasmon resonance. This makes such route appealing for sensing applications since the figure of merit of the Au nanoparticles obtained after thermal evaporation is more than doubled. Such process could besides allow tuning the localized surface plasmon resonance by using copolymer with variou…
We theoretically investigate the creation of a magnetic moment in gold nanoparticles by circularly polarized laser light. To this end, we describe the collective electron dynamics in gold nanoparticles using a semiclassical approach based on a quantum hydrodynamic model that incorporates the prin- cipal quantum many-body and nonlocal effects, such as the electron spill-out, the Hartree potential, and the exchange and correlation effects. We use a variational approach to investigate the breathing and the dipole dynamics induced by an external electric field. We show that gold nanoparticles can …
We present theoretical calculations for the absorption properties of protein-coated gold nanoparticles on graphene and graphite substrates. As the substrate is far away from nanoparticles, numerical results show that the number of protein bovine serum molecules molecules aggregating on gold surfaces can be quantitatively determined for gold nanoparticles with arbitrary size by means of the Mie theory and the absorption spectra. The presence of graphitic substrate near protein-conjugated gold nanoparticles substantially enhances the red shift of the surface plasmon resonances of the nanoparticl…
The ability to partially oxidize methane at low temperatures and pressures would have important environmental and economic applications. Although methane oxidation on gold nanoparticles has been observed experimentally, our density functional theory (DFT) calculations indicate neither CH4, CH3, nor H adsorb on a neutral gold nanoparticle. However, by positively charging gold nanoparticles, e.g. through charge transfer to the TiO2 substrate, CH4 binding increases while O2 binding remains relatively unchanged. We demonstrate that CH4 adsorption is via bonding with the metal s levels. This holds …
Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into the associated mechanisms. However, modern synthesis processes for plasmonic …
Metallic nanoparticles, liquefied by fast laser irradiation, go through a rapid change of shape attempting to minimize their surface energy. The resulting nanodrops may be ejected from the substrate when the mechanisms leading to dewetting are sufficiently strong, as in the experiments involving gold nanoparticles [Habenicht et al., Science 309, 2043 (2005)]. We use a direct continuum-level approach to accurately model the process of liquid nanodrop formation and the subsequent ejection from the substrate. Our computations show a significant role of inertial effects and an elaborate interplay …
The theoretical model of a volcano-type size dependence of extraordinary catalytic activity of gold nanoparticles in CO oxidation is proposed based on the electronic theory of catalysis, the jellium model of metal clusters and the d-band model of formation bonds in transition metals. The kinetics of the general mechanism of CO oxidation reaction catalyzed by gold nanoparticles through dissociative adsorption of oxygen molecules and interaction with CO molecules from the gas-phase is considered by introducing electronic steps into 3-step mechanism of the reaction, corresponding to transitions b…
We developed a microscope intended to probe, using a parallel heterodyne receiver, the fluctuation spectrum of light quasi-elastically scattered by gold nanoparticles diffusing in viscous fluids. The cutoff frequencies of the recorded spectra scale up linearly with those expected from single scattering formalism in a wide range of dynamic viscosities (1 to 15 times water viscosity at room temperature). Our scheme enables ensemble-averaged optical fluctuations measurements over multispeckle recordings in low light, at temporal frequencies up to 10 kHz, with a 12 Hz framerate array detector.
Self-organized collective behaviour of active units is inspiring new designs of artificial swarms of micron-sized objects. However, active control at the nanoscale remains elusive. We have accurately solved the collective optofluidic dynamics of gold plasmonic 50 nm-radius nanoparticles moving in aqueous solution under a nonconservative optical vortex lattice. Above a critical field intensity and concentration, the interplay between optical forces, thermal fluctuations and hydrodynamic pairing leads to a spontaneous transition towards synchronised motion exhibiting a rich assortment of collect…
The dependence of the surface plasmons resonance (SPR) frequency on the size of gold nanoparticles (GNPs) is experimentally studied. The measured data for the SPR frequency by UV-Vis spectroscopy and GNPs diameter by Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM) are collected in the course of classical citrate GNPs synthesis. The relationship between the GNPs size and the blue shift of the light absorption is presented. They are fitted by an equation with a single free parameter, the dielectric permittivity of the surrounding media. Th…
Surface enhanced Raman scattering (SERS) is optically sensitive and chemically specific to detect single molecule spectroscopic signatures. Facilitating this capability in optically-trapped nanoparticles at low laser power remains a significant challenge. In this letter, we show single molecule SERS signatures in reversible assemblies of trapped plasmonic nanoparticles using a single laser excitation (633 nm). Importantly, this trap is facilitated by the thermoplasmonic field of a single gold nanoparticle dropcasted on a glass surface. We employ bi-analyte SERS technique to ascertain the singl…
In this study nanoscale structure and associated energy dissipation behavior of nanoparticulates of tungsten disulphide (WS2) and nanoparticles of gold (Au) were investigated by advanced scanning probe and electron microscopy techniques. WS2 nanoparticulates were deposited on silicon substrate by van der Waals adhesion transfer-deposition mechanisms. The templates of three size variants of Au nanoparticles, close packed (4-6nm), well dispersed (120-150nm) and clusters of (120-150 nm) nanoparticles were prepared on silicon substrates. Nano-microstructure, morphology, topography and phase shift …
We report the investigation of the generation and detection of GHz coherent acoustic phonons in plasmonic gold nanoparticles superlattices (NPS). The experiments have been performed from an optical femtosecond pump-probe scheme across the optical plasmon resonance of the superlattice. Our experiments allow to estimate the collective elastic response (sound velocity) of the NPS as well as an estimate of the nano-contact elastic stiffness. It appears that the light-induced coherent acoustic phonon pulse has a typical in-depth spatial extension of about 45 nm which is roughly 4 times the optical …
Superlubricity, or alternatively termed structural (super)lubrictiy, is a concept where ultra-low friction is expected at the interface between sliding surfaces if these surfaces are incommensurate and thus unable to interlock. In this work, we now report on sudden, reversible, friction changes that have been observed during AFM based nanomanipulation experiments of gold nanoparticles sliding on highly oriented pyrolythic graphite. These effects are can be explained by rotations of the gold nanoparticles within the concept of structural superlubricity, where the occurrence of ultra-low frictio…
The design is suggested, and possible operation parameters are discussed, of an instrument to inspect a skin cancer tumour in the terahertz (THz) range, transferring the image into the infrared (IR) and making it visible with the help of standard IR camera. The central element of the device is the THz-to-IR converter, a Teflon or silicon film matrix with embedded 8.5 nm diameter gold nanoparticles. The use of external THz source for irradiating the biological tissue sample is presumed. The converter's temporal characteristics enable its performance in a real-time scale. The details of design s…
The influence of a patterned substrate on obliquely deposited, exchange biased Co/CoO films was studied. It was found that substrates decorated with nanoparticle patterns provide the option to manipulate the orientation of the magnetic easy axis in obliquely deposited thin films. The complementary methods of SQUID magnetometry and polarized neutron reflectometry were used to disentangle the different contributions to the magnetic hysteresis of such complex magnetic systems.
Understanding the physical and chemical mechanisms occurring during the forming process and operation of an organic resistive memory device is a major issue for better performances. Various mechanisms were suggested in vertically stacked memory structures, but the analysis remains indirect and needs destructive characterization (e.g. cross-section to access the organic layers sandwiched between electrodes). Here, we report a study on a planar, monolayer thick, hybrid nanoparticle/molecule device (10 nm gold nanoparticles embedded in an electro-generated poly(2-thienyl-3,4-(ethylenedioxy)thioph…
We report on hybrid memristive devices made of a network of gold nanoparticles (10 nm diameter) functionalized by tailored 3,4(ethylenedioxy)thiophene (TEDOT) molecules, deposited between two planar electrodes with nanometer and micrometer gaps (100 nm to 10 um apart), and electropolymerized in situ to form a monolayer film of conjugated polymer with embedded gold nanoparticles (AuNPs). Electrical properties of these films exhibit two interesting behaviors: (i) a NDR (negative differential resistance) behavior with a peak/valley ratio up to 17, and (ii) a memory behavior with an ON/OFF current…
We study the magneto-optical response of noble metal nanoparticle clusters. We consider the interaction between the light-induced dipoles of particles. In the presence of a magnetic field, the simplest achiral cluster, a dimer, exhibits circular dichroism (CD). The CD of a dimer depends on the directions of the magnetic field and the light wave vector. The CD of a populous cluster weakly depends on the magnetic field. Upon scattering from the cluster, an incident linearly polarized light with polarization azimuth $φ$, becomes elliptically polarized. The polarization azimuth rotation and ellipt…
The ability to create micro/nano patterns of organic self-assembled monolayers on semiconductor surfaces is crucial for fundamental studies and applications in a number of emerging fields in nanoscience. Here, we demonstrate the patterning of thiol molecular SAMs on oxide-free GaAs surface by dip-pen nanolithography and micro-contact printing, facilitated by a process of surface etching and passivation of the GaAs. A quantitative analysis on the molecular diffusion on GaAs was conducted by examining the writing of nanoscale dot and line patterns by DPN, which agrees well with surface diffusion…
The specific role played by small gold nanoparticles supported on the rutile TiO2(110) surface in the processes of adsorption and dissociation of H2 is discussed. It is demonstrated that the molecular and dissociative adsorption of H2 on Au_n clusters containing n = 1, 2, 8 and 20 atoms depends on cluster size, geometry structure, cluster flexibility and the interaction with the support material. Rutile TiO2(110) support energetically promotes H2 dissociation on gold clusters. It is demonstrated that the active sites towards H2 dissociation are located at corners and edges on the surface of th…
Computational modeling and accurate simulations of localized surface plasmon resonance (LSPR) absorption properties are reported for gold nanobipyramids (GNBs), a class of metal nanoparticle that features highly tunable, geometrydependent optical properties. GNB bicone models with spherical tips performed best in reproducing experimental LSPR spectra while the comparison with other geometrical models provided a fundamental understanding of base shapes and tip effects on the optical properties of GNBs. Our results demonstrated the importance of averaging all geometrical parameters determined fr…
We propose a new approach to understand the time-dependent temperature increasing process of gold-silica core-shell nanoparticles injected into chicken tissues under near-infrared laser irradiation. Gold nanoshells strongly absorb near-infrared radiations and efficiently transform absorbed energy into heat. Temperature rise given by experiments and numerical calculations based on bioheat transfer are in good agreement. Our work improves the analysis of a recent study [Richardson et al., Nano Lett. 9, 1139 (2009)] by including effects of the medium perfusion on temperature increase. The theoret…
Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination o…
We demonstrate that highly-ordered two-dimensional crystals of ligand-capped gold nanoparticles display a local photo-mechanical stiffness as high as that of solids such as graphite. In out-of equilibrium electron diffraction experiments, a strong temperature jump is induced in a thin film with a femtosecond laser pulse. The initial electronic excitation transfers energy to the underlying structural degrees of freedom, with a rate generally proportional to the stiffness of the material. With femtosecond small-angle electron diffraction, we observe the temporal evolution of the diffraction feat…
Surface plasmonic effects of metallic particles have been known to be an effective method to improve the performance light emitting didoes. In this work, we reported the sputtered Au nanoparticles enhanced electroluminescence in inverted quantum dot light emitting diodes (ITO/Au NPs/ZnMgO/QDs/TFB/PEDOT:PSS/Al). By combining the time-resolved photoluminescence, transient electroluminescence and ultraviolet photoelectron spectrometer measurements, the enhancement can be explained to the internal field enhanced exciton coupling to surface plasmons and the increased electron injection rate with Au…
An overarching computational framework unifying several optical theories to describe the temporal evolution of gold nanoparticles (GNPs) during a seeded growth process is presented. To achieve this, we used the inexpensive and widely available optical extinction spectroscopy, to obtain quantitative kinetic data. In situ spectra collected over a wide set of experimental conditions were regressed using the physical model, calculating light extinction by ensembles of GNPs during the growth process. This model provides temporal information on the size, shape, and concentration of the particles and…
The adsorption of hydrogen on Au nanoparticles (NPs) of size of the order of 10 nm has been investigated by use of localised surface plasmon resonances (LSPR) in the NPs. The samples, formed by Au NPs obtained by oblique angle deposition on glass substrates, display a strong optical dichroism due to two different plasmon resonances dependent on the polarisation of light. This ensured the use of Transmittance Anisotropy Spectroscopy, a sensitive derivative optical technique, which permitted one to measure shifts of the LSPR as small as 0.02 nm upon H adsorption, which is not accessible by conve…
