Comprehensive Raman study of epitaxial silicene-related phases on Ag(111).

The investigation of the vibrational properties of epitaxial silicene and two-dimensional (2D) Si structures on the silver(111) surface aims for a better understanding of the structural differences and of the simplification of the seemingly complex phase diagrams reported over the last years. The spectral signatures of the main silicene phases epitaxially grown on Ag(111) were obtained using in situ Raman spectroscopy. Due to the obvious 2D nature of various epitaxial silicene structures, their fingerprints consist of similar sets of Raman modes. The reduced phase diagram also includes other Si phases, such as amorphous and crystalline silicon, which emerge on the Ag surface at low and high preparation temperatures, respectively. The Raman signatures obtained along with their interpretations provide the referential basis for further studies and for potential applications of epitaxial silicene.

Microfluidic setup for on-line SERS monitoring using laser induced nanoparticle spots as SERS active substrate.

A microfluidic setup which enables on-line monitoring of residues of malachite green (MG) using surface-enhanced Raman scattering (SERS) is reported. The SERS active substrate was prepared via laser induced synthesis of silver or gold nanoparticles spot on the bottom of a 200 µm inner dimension glass capillary, by focusing the laser beam during a continuous flow of a mixture of silver nitrate or gold chloride and sodium citrate. The described microfluidic setup enables within a few minutes the monitoring of several processes: the synthesis of the SERS active spot, MG adsorption to the metal surface, detection of the analyte when saturation of the SERS signal is reached, and finally, the desorption of MG from the spot. Moreover, after MG complete desorption, the regeneration of the SERS active spot was achieved. The detection of MG was possible down to 10-7 M concentration with a good reproducibility when using silver or gold spots as SERS substrate.

Transparent conducting oxide induced by liquid electrolyte gating.

Optically transparent conducting materials are essential in modern technology. These materials are used as electrodes in displays, photovoltaic cells, and touchscreens; they are also used in energy-conserving windows to reflect the infrared spectrum. The most ubiquitous transparent conducting material is tin-doped indium oxide (ITO), a wide-gap oxide whose conductivity is ascribed to n-type chemical doping. Recently, it has been shown that ionic liquid gating can induce a reversible, nonvolatile metallic phase in initially insulating films of WO3 Here, we use hard X-ray photoelectron spectroscopy and spectroscopic ellipsometry to show that the metallic phase produced by the electrolyte gating does not result from a significant change in the bandgap but rather originates from new in-gap states. These states produce strong absorption below ∼1 eV, outside the visible spectrum, consistent with the formation of a narrow electronic conduction band. Thus WO3 is metallic but remains colorless, unlike other methods to realize tunable electrical conductivity in this material. Core-level photoemission spectra show that the gating reversibly modifies the atomic coordination of W and O atoms without a substantial change of the stoichiometry; we propose a simple model relating these structural changes to the modifications in the electronic structure. Thus we show that ionic liquid gating can tune the conductivity over orders of magnitude while maintaining transparency in the visible range, suggesting the use of ionic liquid gating for many applications.

Ferromagnetic Mn-Implanted GaP: Microstructures vs Magnetic Properties.

Ferromagnetic GaMnP layers were prepared by ion implantation and pulsed laser annealing (PLA). We present a systematic investigation on the evolution of microstructure and magnetic properties depending on the pulsed laser annealing energy. The sample microstructure was analyzed by high-resolution X-ray diffraction (HR-XRD), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), ultraviolet Raman spectroscopy (UV-RS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of X-ray Pendellösung fringes around GaP (004) and RBS channeling prove the epitaxial structure of the GaMnP layer annealed at the optimized laser energy density (0.40 J/cm(2)). However, a forbidden TO vibrational mode of GaP appears and increases with annealing energy, suggesting the formation of defective domains inside the layer. These domains mainly appear in the sample surface region and extend to almost the whole layer with increasing annealing energy. The reduction of the Curie temperature (TC) and of the uniaxial magnetic anisotropy gradually happens when more defects and the domains appear as increasing the annealing energy density. This fact univocally points to the decisive role of the PLA parameters on the resulting magnetic characteristics in the processed layers, which eventually determine the magnetic (or spintronics) figure of merit.

Optical properties and bandgap evolution of ALD HfSiOx films.

Hafnium silicate films with pure HfO2 and SiO2 samples as references were fabricated by atomic layer deposition (ALD) in this work. The optical properties of the films as a function of the film composition were measured by vacuum ultraviolet (VUV) ellipsometer in the energy range of 0.6 to 8.5 eV, and they were investigated systematically based on the Gaussian dispersion model. Experimental results show that optical constants and bandgap of the hafnium silicate films can be tuned by the film composition, and a nonlinear change behavior of bandgap with SiO2 fraction was observed. This phenomenon mainly originates from the intermixture of d-state electrons in HfO2 and Si-O antibonding states in SiO2.

Carbon p electron ferromagnetism in silicon carbide.

Ferromagnetism can occur in wide-band gap semiconductors as well as in carbon-based materials when specific defects are introduced. It is thus desirable to establish a direct relation between the defects and the resulting ferromagnetism. Here, we contribute to revealing the origin of defect-induced ferromagnetism using SiC as a prototypical example. We show that the long-range ferromagnetic coupling can be attributed to the p electrons of the nearest-neighbor carbon atoms around the VSiVC divacancies. Thus, the ferromagnetism is traced down to its microscopic electronic origin.

Surface-enhanced Raman scattering by colloidal CdSe nanocrystal submonolayers fabricated by the Langmuir-Blodgett technique.

We present the results of an investigation of surface-enhanced Raman scattering (SERS) by optical phonons in colloidal CdSe nanocrystals (NCs) homogeneously deposited on both arrays of Au nanoclusters and Au dimers using the Langmuir-Blodgett technique. The coverage of the deposited NCs was less than one monolayer, as determined by transmission and scanning electron microscopy. SERS by optical phonons in CdSe nanocrystals showed a significant enhancement that depends resonantly on the Au nanocluster and dimer size, and thus on the localized surface plasmon resonance (LSPR) energy. The deposition of CdSe nanocrystals on the Au dimer nanocluster arrays enabled us to study the polarization dependence of SERS. The maximal SERS signal was observed for light polarization parallel to the dimer axis. The polarization ratio of the SERS signal parallel and perpendicular to the dimer axis was 20. The SERS signal intensity was also investigated as a function of the distance between nanoclusters in a dimer. Here the maximal SERS enhancement was observed for the minimal distance studied (about 10 nm), confirming the formation of SERS "hot spots".

Raman spectroscopy insights into the size-induced structural transformation in SnSe nanolayers.

Raman spectroscopy is used to probe the structural changes in [SnSe]m[MoSe2]n ferecrystal thin films as a function of m, the number of bilayers of SnSe. In spite of the interleaved structure in the intergrowths, Raman spectra can be described as a superposition of spectra from the individual components, indicating that the interaction at the interface between the components is relatively weak. Analysis of room-temperature Raman spectra indicate that the MoSe2 layers separating the SnSe layers are nanocrystalline in all of the samples studied, with little change as the number of Se-Mo-Se trilayers (n) or SnSe bilayers (m) increases, reflecting the rotational disorder between adjacent trilayers. A thickness-dependent, continuous transition occurs in the SnSe layer as m is increased, from a pseudotetragonal structure when the layers are thin to a bulk-like orthorhombic SnSe structure when the SnSe layer thickness is increased. Polarization analysis of the Raman scattering from these materials allows the symmetry evolution of the SnSe layers through this transition to be determined.

Photoluminescence emission and Raman response of monolayer MoS2, MoSe2, and WSe2.

We mechanically exfoliate mono- and few-layers of the transition metal dichalcogenides molybdenum disulfide, molybdenum diselenide, and tungsten diselenide. The exact number of layers is unambiguously determined by atomic force microscopy and high-resolution Raman spectroscopy. Strong photoluminescence emission is caused by the transition from an indirect band gap semiconductor of bulk material to a direct band gap semiconductor in atomically thin form.

Nanoscale optical and electrical characterization of horizontally aligned single-walled carbon nanotubes.

During the recent years, a significant amount of research has been performed on single-walled carbon nanotubes (SWCNTs) as a channel material in thin-film transistors (Pham et al. IEEE Trans Nanotechnol 11:44-50, 2012). This has prompted the application of advanced characterization techniques based on combined atomic force microscopy (AFM) and Raman spectroscopy studies (Mureau et al. Electrophoresis 29:2266-2271, 2008). In this context, we use confocal Raman microscopy and current sensing atomic force microscopy (CS-AFM) to study phonons and the electronic transport in semiconducting SWCNTs, which were aligned between palladium electrodes using dielectrophoresis (Kuzyk Electrophoresis 32:2307-2313, 2011). Raman imaging was performed in the region around the electrodes on the suspended CNTs using several laser excitation wavelengths. Analysis of the G+/G- splitting in the Raman spectra (Sgobba and Guldi Chem Soc Rev 38:165-184, 2009) shows CNT diameters of 2.5 ± 0.3 nm. Neither surface modification nor increase in defect density or stress at the CNT-electrode contact could be detected, but rather a shift in G+ and G- peak positions in regions with high CNT density between the electrodes. Simultaneous topographical and electrical characterization of the CNT transistor by CS-AFM confirms the presence of CNT bundles having a stable electrical contact with the transistor electrodes. For a similar load force, reproducible current-voltage (I/V) curves for the same CNT regions verify the stability of the electrical contact between the nanotube and the electrodes as well as the nanotube and the AFM tip over different experimental sessions using different AFM tips. Strong variations observed in the I/V response at different regions of the CNT transistor are discussed.

Temperature-dependent Raman investigation of rolled up InGaAs/GaAs microtubes.

Large arrays of multifunctional rolled-up semiconductors can be mass-produced with precisely controlled size and composition, making them of great technological interest for micro- and nano-scale device fabrication. The microtube behavior at different temperatures is a key factor towards further engineering their functionality, as well as for characterizing strain, defects, and temperature-dependent properties of the structures. For this purpose, we probe optical phonons of GaAs/InGaAs rolled-up microtubes using Raman spectroscopy on defect-rich (faulty) and defect-free microtubes. The microtubes are fabricated by selectively etching an AlAs sacrificial layer in order to release the strained InGaAs/GaAs bilayer, all grown by molecular beam epitaxy. Pristine microtubes show homogeneity of the GaAs and InGaAs peak positions and intensities along the tube, which indicates a defect-free rolling up process, while for a cone-like microtube, a downward shift of the GaAs LO phonon peak along the cone is observed. Formation of other type of defects, including partially unfolded microtubes, can also be related to a high Raman intensity of the TO phonon in GaAs. We argue that the appearance of the TO phonon mode is a consequence of further relaxation of the selection rules due to the defects on the tubes, which makes this phonon useful for failure detection/prediction in such rolled up systems. In order to systematically characterize the temperature stability of the rolled up microtubes, Raman spectra were acquired as a function of sample temperature up to 300°C. The reversibility of the changes in the Raman spectra of the tubes within this temperature range is demonstrated.

Carbon/carbon nanocomposites fabricated by base catalyzed twin polymerization of a Si-spiro compound on graphite sheets.

Defect-free microporous carbon layers on graphite can be produced by DABCO-catalyzed twin polymerization of 2,2'-spirobi[4H-1,3,2-benzodioxasiline] in a slurry polymerization and subsequent thermal transformation of the resulting phenolic resin into carbon.

On pattern transfer in replica molding.

Nano- and micromolding of elastic materials produces smoothed replicas of the mold structures. This limits the technique's resolution. Here we identified surface tension as the cause of smoothing and derived explicit equations for calculating molded feature shapes. The characteristic length scale for smoothing is given by the ratio of the interface tension to Young's modulus of the molded material. This approach offers the possibility to correct for the smoothing caused by surface tension during mold design. Moreover, it can be exploited to measure interface tension.