Search

We report the effects of a laser-oxidized single layer graphene (SLG) surface on the self-assembly of amphiphilic gelator N-fluorenylmethoxycarbonyl-L-phenylalanine (Fmoc-Phe) towards an gel–SLG interface. Laser oxidation modulates the levels of hydrophobicity/hydrophilicity on the SLG surface. Atomic force, scanning electron, helium ion and scattering scanning nearfield optical microscopies (AFM, SEM, HIM, s-SNOM) were employed to assess the effects of surface properties on the secondary and tertiary organization of the formed Fmoc-Phe fibres at the SLG–gel interface. S-SNOM shows sheet-like secondary structures on both hydrophobic/hydrophilic areas of SLG and helical or disordered structures mainly on the hydrophilic oxidized surface. The gel network heterogeneity on pristine graphene was observed at the scale of single fibres by s-SNOM, demonstrating its power as a unique tool to study supramolecular assemblies and interfaces at nanoscale. Our findings underline the sensitivity of assembled structures to surface properties, while our characterization approach is a step forward in assessing surface–gel interfaces for the development of bionic devices. peerReviewed

Realization of Fano resonance in plasmonic oligomers is often exploited to design efficient plasmonic substrates for surface-enhanced coherent anti-Stokes Raman scattering. Disk-type Fano-resonant plasmonic oligomers are widely used to enhance the Raman signal of the probe material. Generally, hot spots are generated in those oligomers at different spatial locations at different wavelengths and only a few spatially overlapping hot spots at multiple wavelengths can be achieved with oblique incidence of excitation light. In this work, we proposed hexagonal gold nanoparticle based Fano-resonant plasmonic oligomers that can yield higher number of spatially overlapped hot spots compared to the disk type oligomers even with the normal incidence of excitation light. The oligomers were numerically modelled and optimized for surface-enhanced coherent anti-Stokes Raman scattering with 780 nm pumping and 500–1800 cm− 1 Raman signature region. The Fano lineshape was engineered to ensure near-field energy coupling at pump while enhancing the coherent anti-Stokes Raman signal at the far field. Our computational studies explored the purely electric origin of Fano resonance in those oligomers and provided maximum Raman enhancements of 1012–1013 from them to enable single-molecular level applications. Our findings provide a way to realize fabrication-friendly nanostructures with higher number of spatially localized hotspots for improving the Raman detection sensitivity.

The production of negative ions in cesium sputter ion sources is generally considered to be a pure surface process. It has been recently proposed that ion pair production could explain the higher-than-expected beam currents extracted from these ion sources, therefore opening the door for laser-assisted enhancement of the negative ion yield. We have tested this hypothesis by measuring the effect of various pulsed diode lasers on the O$^-$ beam current produced from Al$_2$O$_3$ cathode of a cesium sputter ion source. It is expected that the ion pair production of O$^-$ requires populating the 5d electronic states of neutral cesium, thus implying that the process should be provoked only with specific wavelengths. Our experimental results provide evidence for the existence of a wavelength-dependent photo-assisted effect but cast doubt on its alleged resonant nature as the prompt enhancement of beam current can be observed with laser wavelengths exceeding a threshold photon energy. The beam current transients observed during the laser pulses suggest that the magnitude and longevity of the beam current enhancement depends on the cesium balance on the cathode surface. We conclude that the photo-assisted negative ion production could be of practical importance as it can more than double the extracted beam current under certain operational settings of the ion source., Comment: 12 pages, 13 figures

We construct a model describing the response of a hybrid system where the electromagnetic field - in particular, surface plasmon polaritons - couples strongly with electronic excitations of atoms or molecules. Our approach is based on the input-output theory of quantum optics, and in particular it takes into account the thermal and quantum vibrations of the molecules. The latter is described within the $P(E)$ theory analogous to that used in the theory of dynamical Coulomb blockade. As a result, we are able to include the effect of the molecular Stokes shift on the strongly coupled response of the system. Our model then accounts for the asymmetric emission from upper and lower polariton modes. It also allows for an accurate description of the partial decoherence of the light emission from the strongly coupled system. Our results can be readily used to connect the response of the hybrid modes to the emission and fluorescence properties of the individual molecules, and thus are relevant in understanding any utilization of such systems, like coherent light harvesting., 13 pages, 6 figures; included comparison between theory and experiment

While it is well established that elevated temperatures can induce surface roughening of metal surfaces, the effect of a high electric field on the atomic structure at ambient temperature has not been investigated in detail. Here we show with atomic resolution using in situ transmission electron microscopy how intense electric fields induce reversible switching between perfect crystalline and disordered phases of gold surfaces at room temperature. Ab initio molecular dynamics simulations reveal that the mechanism behind the structural change can be attributed to a vanishing energy cost in forming surface defects in high electric fields. Our results demonstrate how surface processes can be directly controlled at the atomic scale by an externally applied electric field, which promotes an effective decoupling of the topmost surface layers from the underlying bulk. This opens up opportunities for development of active nanodevices in e.g. nanophotonics and field-effect transistor technology as well as fundamental research in materials characterization and of yet unexplored dynamically-controlled low-dimensional phases of matter., Comment: The manuscript is 10 pages long and the supplemental material is 15 pages. There are six supplemental movies that can be provided upon request to LDK

This thesis reports a novel approach for purification of carbon nanotube (CNT) samples deposited on smooth silicon substrates through a mobile liquid interface interacting with carbonaceous debris particles that contaminate the deposition. The method is based on physical interaction of the particles and the three-phase contact line via capillary interface forces, i.e. the surface tension, which results in the detachment of chemically indispersible colloids from the sample surface. In the experiments reported in this work, we focus primarily on arc-discharge grown multi-walled carbon nanotubes, whose synthesis is particularly plagued by carbonaceous debris that is difficult to remove without harsh chemical treatments. The irregular debris particles are preferentially captured by the mobile contact line, while tubular CNTs are retained in large numbers due to their appreciably stronger adhesion. Our cleaning method has the added benefit that the intrinsic chemical properties of the CNTs are fully preserved, since no chemical treatments are needed; only prerequisite is the hydrophilic treatment of the underlying substrate, which on silicon wafers can be accomplished through oxygen plasma. Various aspects of the cleaning process, including the effects of contact line velocity, chemical composition of the immersion liquid, and the CNT orientation relative to the liquid front are investigated in this thesis. Furthermore, atomic force microscopy (AFM) imaging and the image analysis methodology is discussed. Ad- ditionally, we demonstrate some research applications that directly benefit from our technique, e.g. microraman spectroscopy of individual carbon nanotubes, and nanomechanical investigation of suspended tubes via AFM-deflection measurements. Theoretical treatment of the detachment process is presented in the framework developed for spherical microcolloids in existing works. In this model, the particle detachment is primarily attributed to the surface tension force. Other forces affecting the process include adhesion, which in liquid electrolyte medium can be estimated via the DLVO adhesion theory, and hydrophobic interactions. We conclude that the particle detachment is qualitatively well-explained by the physical interactions at the contact line, while the selectivity of the process for the irregular debris particles in favor of the tubular CNTs probably stems from differences in the magnitude of the adhesion force. Chemical factors associated with the composition of the immersion liquid on the other hand seem to only have very limited effect on the quantitative cleaning result. Regarding to detachment of CNTs, orientation-dependent behavior is implied, with species oriented perpendicular to the advancing contact line reflecting the greatest probability to be retained. Overall, the detachment of all particles is found to increase with decreasing velocity of the liquid interface. These results are generally in qualitative agreement with existing works dealing with spherical microcolloids