Surface- and tip-enhanced resonant Raman scattering from CdSe nanocrystals.

Surface- and tip-enhanced resonant Raman scattering (resonant SERS and TERS) by optical phonons in a monolayer of CdSe quantum dots (QDs) is demonstrated. The SERS enhancement was achieved by employing plasmonically active substrates consisting of gold arrays with varying nanocluster diameters prepared by electron-beam lithography. The magnitude of the SERS enhancement depends on the localized surface plasmon resonance (LSPR) energy, which is determined by the structural parameters. The LSPR positions as a function of nanocluster diameter were experimentally determined from spectroscopic micro-ellipsometry, and compared to numerical simulations showing good qualitative agreement. The monolayer of CdSe QDs was deposited by the Langmuir-Blodgett-based technique on the SERS substrates. By tuning the excitation energy close to the band gap of the CdSe QDs and to the LSPR energy, resonant SERS by longitudinal optical (LO) phonons of CdSe QDs was realized. A SERS enhancement factor of 2 × 10(3) was achieved. This allowed the detection of higher order LO modes of CdSe QDs, evidencing the high crystalline quality of QDs. The dependence of LO phonon mode intensity on the size of Au nanoclusters reveals a resonant character, suggesting that the electromagnetic mechanism of the SERS enhancement is dominant. Finally, the resonant TERS spectrum from CdSe QDs was obtained using electrochemically etched gold tips providing an enhancement on the order of 10(4). This is an important step towards the detection of the phonon spectrum from a single QD.

Colloidal ZnO nanocrystals in dimethylsulfoxide: a new synthesis, optical, photo- and electroluminescent properties.

Stable colloidal solutions of zinc oxide in dimethylsulfoxide were synthesized via interaction between zinc(II) acetate and tetraalkylammonium hydroxides (alkyl-ethyl, propyl, butyl, and pentyl). Colloids of ZnO emit photoluminescence in a broad band with a maximum at 2.3-2.4 eV with quantum yields of up to 9-10% at room temperature and 15-16% at 80 K. The photoluminescence is supposed to originate from the radiative recombination of conduction band electrons with holes captured by deep traps having corresponding states in the band gap 1.0-1.2 eV above the valence band edge. The size of colloidal ZnO nanocrystals depends on the duration and temperature of the post-synthesis treatment and varies in the range of 3-6 nm. Growth of the ZnO nanocrystals can be terminated at any moment of the thermal treatment by freezing the colloidal solution or by addition of tetraethyl orthosilicate which hydrolyses forming core-shell ZnO@SiO2 particles. ZnO nanocrystals introduced into polyethyleneimine films can be used as an active component of an LED emitting at an applied voltage higher than 13 V.

Gold nanoparticles generated by thermolysis of "all-in-one" gold(I) carboxylate complexes.

Consecutive synthesis methodologies for the preparation of the gold(I) carboxylates [(Ph(3)P)AuO(2)CCH(2)(OCH(2)CH(2))(n)OCH(3)] (n = 0-6) (6a-g) are reported, whereby selective mono-alkylation of diols HO(CH(2)CH(2)O)(n)H (n = 0-6), Williamson ether synthesis and metal carboxylate (Ag, Au) formation are the key steps. Single crystal X-ray diffraction studies of 6a (n = 0) and 6b (n = 1) were carried out showing that the P-Au-O unit is essentially linear. These compounds were applied in the formation of gold nanoparticles (NP) by a thermally induced decomposition process and hence the addition of any further stabilizing and reducing reagents, respectively, is not required. The ethylene glycol functionalities, providing multiple donating capabilities, are able to stabilise the encapsulated gold colloids. The dependency of concentration, generation time and ethylene glycol chain lengths on the NP size and size distribution is discussed. Characterisation of the gold colloids was performed by TEM, UV/Vis spectroscopy and electron diffraction studies revealing that Au NP are formed with a size of 3.3 (±0.6) to 6.5 (±0.9) nm in p-xylene with a sharp size distribution. Additionally, a decomposition mechanism determined by TG-MS coupling experiments of the gold(i) precursors is reported showing that 1(st) decarboxylation occurs followed by the cleavage of the Au-PPh(3) bond and finally release of ethylene glycol fragments to give Au-NP and the appropriate organics.

Compact metal probes: a solution for atomic force microscopy based tip-enhanced Raman spectroscopy.

There are many challenges in accomplishing tip-enhanced Raman spectroscopy (TERS) and obtaining a proper tip is probably the greatest one. Since tip size, composition, and geometry are the ultimate parameters that determine enhancement of intensity and lateral resolution, the tip becomes the most critical component in a TERS experiment. However, since the discovery of TERS the cantilevers used in atomic force microscopy (AFM) have remained basically the same: commercial silicon (or silicon nitride) tips covered by a metallic coating. The main issues of using metal-coated silicon cantilevers, such as wearing off of the metal layer or increased tip radius, can be completely overcome by using all-metal cantilevers. Until now in TERS experiments such probes have only been used in a scanning tunneling microscope or in a tuning fork-based shear force microscope but not in AFM. In this work for the first time, we show the use of compact silver cantilevers that are fully compatible with contact and tapping modes in AFM demonstrating their superb performance in TERS experiments.

Magnetic films on nanoperforated templates: a route towards percolated perpendicular media.

We present a study on the magnetization reversal in Co/Pt multilayer films with an out-of-plane easy axis of magnetization deposited onto substrates with densely distributed perforations with an average period as small as 34 nm. Deposition of magnetic Co/Pt multilayers onto the nanoperforated surface results in an array of magnetic nanodots surrounded by a continuous magnetic film. Following the evolution of the magnetic domain pattern in the system, we suggest that domain walls are pinned on structural inhomogeneities given by the underlying nanoperforated template. Furthermore, a series of micromagnetic simulations was performed in order to understand the modification of the pinning strength of domain walls due to the magnetic interaction between nanodots and the surrounding film. The results of the simulations show that magnetic exchange coupling between the nanodots and the surrounding film strongly influences the pinning behavior of the magnetic domain walls which can be optimized to provide maximal pinning.

Atomic layer deposition (ALD) as a coating tool for reinforcing fibers.

Layers of alumina were deposited on to bundled carbon fibers in an atomic layer deposition (ALD) process via sequential exposure to vapors of aluminium chloride and water, respectively. Scanning electron microscopic (SEM) images of the coated fibers revealed that each individual fiber within a bundle was coated evenly and separately, fibers are not bridged by the coating. SEM and transmission electron microscopic (TEM) images indicate that the coating was uniform and conformal with good adhesion to the fiber surface. Average deposition rate, measured from SEM images, was 0.06 nm per cycle at 500 °C. SEM also revealed that at deposition temperatures of 500 °C few of the fibers were damaged. At temperatures of 300 °C, no damaged fibers were observed, the average deposition rate decreased down to 0.033 nm per cycle. Oxidation resistance of the alumina-coated fibers was characterized by thermogravimetric analysis (TGA). The alumina coating improved oxidation resistance of the carbon fiber significantly. Oxidation onset temperature was 600 °C for fibers coated with a 45 nm thick alumina. Uncoated fibers, on the other hand, started to oxidize at temperatures as low as 250 °C.

Feedforward correction of nonlinearities in piezoelectric scanner constructions and its experimental verification.

Piezoelectrical actuators widely used in scanning devices for highly resolved displacement generation exhibit a number of known nonlinear effects as hysteresis and creep. This article describes an attempt to minimize those nonlinearities by recognizing the relation between scan range and voltage magnitude in a scanner specific function. In addition, by utilizing a strain gauge sensor system, a forward displacement correction is realized. The mathematical procedure behind the hysteresis correction is described in detail. The dependence of the higher order correction factors on parameters such as scan speed, scan range, or center position is studied carefully to extract their influence on the result. Finally, integral nonlinearities of about 1% are proven in experiments with an atomic force microscope.

Propagation of femtosecond light pulses through near-field optical aperture probes.

The propagation of femtosecond light pulses through near-field optical fiber tips has been modelled numerically in three spatial dimensions by means of the finite integration technique. Ideally conducting as well as real metallic coatings of the tip have been considered, and the influence of surface plasmon polaritons (SPP) on shape, spectrum, and amplitude of the light pulse in the near and far fields of the tip have been investigated in this way. Special attention has been devoted to the superluminal tunneling of light through the fiber tip. The variation of phase and group velocities along the fiber axis has been characterized for a number of real metals and for different tip angles. A maximum of both velocities in the near field of the tip is characteristic for coatings of finite conductivity. For some tip angles negative values of the phase and/or group velocities are observed, which are caused by the propagation of SPP on the outer surface of the coating and their conversion into photons. It is shown, that the excitation of SPP on the metallic coating leads to strongly altered spatial emission characteristics of the tip.