Free carrier enhanced depletion in ZnO nanorods decorated with bimetallic AuPt nanoclusters.

The decoration of semiconductor nanostructures with small metallic clusters usually leads to an improvement of their properties in sensing or catalysis. Bimetallic cluster decoration typically is claimed to be even more effective. Here, we report a detailed investigation of the effects of Au, Pt or AuPt nanocluster decoration of ZnO nanorods on charge transport, photoluminescence and UV sensitivity. ZnO nanorods were synthesized by chemical bath deposition while decoration with small nanoclusters (2-3 nm in size) was achieved by a laser-ablation based cluster beam deposition technology. The structural properties were investigated by scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry, and the optoelectronic properties by current-voltage and photoluminescence measurements. The extent of band bending at the cluster-ZnO interface was quantitatively modeled through numerical simulations. The decoration of ZnO nanorods with monometallic Au or Pt nanoclusters causes a significant depletion of free electrons below the surface, leading to a reduction of UV photoluminescence, an increase of ZnO nanorod dark resistance (up to 200 times) and, as a consequence, an improved sensitivity (up to 6 times) to UV light. These effects are strongly enhanced (up to 450 and 10 times, respectively) when ZnO nanorods are decorated with bimetallic AuPt nanoclusters that substantially augment the depletion of free carriers likely due to a more efficient absorption of the gas molecules on the surface of the bimetallic AuPt nanoclusters than on that of their monometallic counterparts. The depletion of free carriers in cluster decorated ZnO nanorods is quantitatively investigated and modelled, allowing the application of these composite materials in UV sensing and light induced catalysis.

L10-FeNi films on Au-Cu-Ni buffer-layer: a high-throughput combinatorial study.

The fct L10-FeNi alloy is a promising candidate for the development of high performance critical-elements-free magnetic materials. Among the different materials, the Au-Cu-Ni alloy has resulted very promising; however, a detailed investigation of the effect of the buffer-layer composition on the formation of the hard FeNi phase is still missing. To accelerate the search of the best Au-Cu-Ni composition, a combinatorial approach based on High-Throughput (HT) experimental methods has been exploited in this paper. HT magnetic characterization methods revealed the presence of a hard magnetic phase with an out-of-plane easy-axis, whose coercivity increases from 0.49 kOe up to 1.30 kOe as the Au content of the Cu-Au-Ni buffer-layer decreases. Similarly, the out-of-plane magneto-crystalline anisotropy energy density increases from 0.12 to 0.35 MJ/m3. This anisotropy is attributed to the partial formation of the L10 FeNi phase induced by the buffer-layer. In the range of compositions we investigated, the buffer-layer structure does not change significantly and the modulation of the magnetic properties with the Au content in the combinatorial layer is mainly related to the different nature and extent of interlayer diffusion processes, which have a great impact on the formation and order degree of the L10 FeNi phase.

Selective synthesis of turbostratic polyhedral carbon nano-onions by arc discharge in water.

Carbon nano-onions (CNOs), in their spherical or polyhedral forms, represent an important class of nanomaterials, due to their peculiar physical and electrochemical properties. Among the different methods of production, arc discharge between graphite electrodes sustained by deionized water is one of the most promising to obtain good quality CNOs in gram quantities. We applied the method with the aim to optimize the production of CNOs, using an innovative experimental arrangement. The discharges generate dispersed nanomaterials and a black hard cathodic deposit, which were studied by transmission electron microscopy-high-resolution TEM, scanning electron microscopy, Raman, thermogravimetric analysis and energy-dispersive x-ray spectroscopy. A simple mechanical grinding of the deposits permitted us to obtain turbostratic polyhedral CNOs that exhibited higher stability towards burning in air, compared to CNOs found in water. We propose a mechanism for the formation of the CNOs present in the deposit, in which the crystallization is driven by a strong temperature gradient existing close to the cathode surface at the beginning of the process, and subsequently close to the deposit surface whenever it is growing.

Anisotropic extended misfit dislocations in overcritical SiGe films by local substrate patterning.

In this work we will show how local substrate patterning leads to a long range controlled propagation of dislocations in SiGe films grown on Si(001) substrates. Dislocations preferentially nucleate in the inhomogeneous strain field associated with the patterned pits, and then partialize on the local (111) surfaces which form the pit sidewalls. The resulting V-shaped defects extend for several microns and effectively block the propagation of randomly nucleated dislocations which propagate in the perpendicular direction. The surface morphology and strain fields associated with the extended defects have been characterized by atomic force microscopy and µRaman spectroscopy, and the defects have been directly observed with high resolution transmission electron microscopy.

Coalescence of silver clusters by immersion in diluted HF solution.

The galvanic displacement deposition of silver on H-terminated Si (100) in the time scale of seconds is instantaneous and characterized by a cluster density of 10(11)-10(12) cm(-2). The amount of deposited Ag follows a t(1/2) dependence in agreement with a Cottrell diffusion limited mechanism. At the same time, during the deposition, the cluster density reduces by a factor 5. This behavior is in contrast with the assumption of immobile clusters. We show in the present work that coalescence and aggregation occur also in the samples immersed in the diluted hydrofluoric acid (HF) solution without the presence of Ag(+). Clusters agglomerate according to a process of dynamic coalescence, typical of colloids, followed by atomic redistribution at the contact regions with the generation of multiple internal twins and stacking-faults. The normalized size distributions in terms of r/rmean follow also the prediction of the Smoluchowski ripening mechanism. No variation of the cluster density occurs for samples immersed in pure H2O solution. The different behavior might be associated to the strong attraction of clusters to oxide-terminated Si surface in presence of water. The silver clusters are instead weakly bound to hydrophobic H-terminated Si in presence of HF. HF causes then the detachment of clusters and a random movement on the silicon surface with mobility of about 10(-13) cm(2)/s. Attractive interaction (probably van der Waals) among particles promotes coarsening.

The role of the interface in germanium quantum dots: when not only size matters for quantum confinement effects.

Quantum confinement (QC) typically assumes a sharp interface between a nanostructure and its environment, leading to an abrupt change in the potential for confined electrons and holes. When the interface is not ideally sharp and clean, significant deviations from the QC rule appear and other parameters beyond the nanostructure size play a considerable role. In this work we elucidate the role of the interface on QC in Ge quantum dots (QDs) synthesized by rf-magnetron sputtering or plasma enhanced chemical vapor deposition (PECVD). Through a detailed electron energy loss spectroscopy (EELS) analysis we investigated the structural and chemical properties of QD interfaces. PECVD QDs exhibit a sharper interface compared to sputter ones, which also evidences a larger contribution of mixed Ge-oxide states. Such a difference strongly modifies the QC strength, as experimentally verified by light absorption spectroscopy. A large size-tuning of the optical bandgap and an increase in the oscillator strength occur when the interface is sharp. A spatially dependent effective mass (SPDEM) model is employed to account for the interface difference between Ge QDs, pointing out a larger reduction in the exciton effective mass in the sharper interface case. These results add new insights into the role of interfaces on confined systems, and open the route for reliable exploitation of QC effects.

Combined strategy to realize efficient photoelectrodes for low temperature fabrication of dye solar cells.

We implemented a low-temperature approach to fabricate efficient photoanodes for dye-sensitized solar cells, which combines three different nanoarchitectures, namely, a highly conductive and highly transparent AZO film, a thin TiO2-blocking layer, and a mesoporous TiO2 nanorod-based working electrode. All the components were processed at T≤200°C. Both the AZO and the TiO2 blocking layers were deposited by reactive sputtering, whereas the TiO2 nanorods were synthesized by surfactant-assisted wet-chemical routes and processed into photoelectrodes in which the native geometric features assured uniform mesoporous structure with effective nanocrystal interconnectivity suitable to maximize light harvesting and electron diffusion. Because of the optimized structure of the TiO2-blocking/AZO bilayer, and thanks to the good adhesion of the TiO2 nanorods over it, a significant enhancement of the charge recombination resistance was demonstrated, this laying on the basis of the outstanding power conversion efficiency achievable through the use of this photoanode's architecture: a value of 4.6% (N719) was achieved with a 4-µm-thick electrode processed at T=200°C. This value noticeably overcomes the current literature limit got on AZO-based cells (N719), which instead use Nb-doped and thicker blocking layers, and thicker nanostructured photoanodes, which have been even sintered at higher temperatures (450-500°C).

Novel approach to the fabrication of Au/silica core-shell nanostructures based on nanosecond laser irradiation of thin Au films on Si.

We demonstrate the possibility of producing Au/SiO(2) core-shell nanoparticles by nanosecond laser irradiation of thin (5 and 20 nm) Au films on Si. The Au/Si eutectic reaction and dewetting process caused by the fast melting and solidification dynamics induced by the nanosecond laser irradiations are investigated as the origin of the formation of core-shell nanoparticles. Using several microscopic techniques (Rutherford backscattering spectrometry, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and energy filtered transmission electron microscopy) the formation and evolution of the core-shell structures are investigated as a function of the laser fluence in the 500-1500 mJ cm(-2) range for both film thicknesses. In particular, the mean height and diameter and surface density evolution of the core-shell structures are quantified and correlated to the laser fluence and Au film thickness.

Biomimetic sensing layer based on electrospun conductive polymer webs.

The aim of the present study is to combine a bio-inspired nanofibrous artificial epithelium to the electronic nose (e-nose) principles. The sensing device set up was an electronic nose consisting of an array of 9 micro-chemoresistors (Cr-Au, 3×3) coated with electrospun nanofibrous structures. These were comprised of doped polyemeraldine base blended with 3 different polymers: polyethylene oxide, polyvinilpyrrolidone and polystyrene, which acted as carriers for the conducting polymer and were the major responsible of the features of each fibrous overlay (electrical parameters, selectivity and sensitivity ranges). The two sensing strategies here adopted and compared consisted in the use of 2 different textural coatings: a single- and a double-overlay, where the double-overlay resulting from overdeposition of 2 different polymer blends. Such e-nose included a plurality of nanofibres whose electrical parameters were at the same time depending on each polymer exposure to analytes (NO(2), NH(3)) and on the spatial distribution of the interlacing fibres. The morphology of the coating arrangements of this novel e-nose was investigated by scanning electron microscopy (SEM) and its sensor responses were processed by multicomponent data analyses (PCA and PLS) reporting encouraging results for detection and recognition of analytes at ppb levels.

High Resolution Measurements of Two-dimensional Dopant Diffusion in Silicon.

We report detailed experimental results on the electrochemical selective etching of doped Si. By using transmission electron microscopy analyses and spreading resistance measurements we investigated the dependence of the etching selectivity on the different parameters of the electrochemical cell, i.e., bias voltage and chemical solution. In B-doped samples immersed in buffered HF, the increase of bias voltage from 0.5 to 1 V produces a slight improvement of the etching selectivity and a B concentration as low as 1 x 10(17) cm(-3) can be successfully delineated at 1 V. A further improvement is achieved by using HF:HNO(3):CH(3)COOH or HF:HCl chemical mixtures for which the delineation sensitivity approaches the value of 1 x 10(16) cm(-3). In buffered HF As-doped regions can be delineated to a concentration of 2 x 10(17) cm(-3), independently of the bias voltage, in the range 2-4 V. These results were used to measure the 2D doping diffusion profiles in silicon wafers patterned with polycrystalline Si strips and implanted with As or B, by using different tilt and twist angles. The high resolution of the electrochemical delineation allowed us to evaluate very accurately the effects of the implant angles on the lateral doping distribution.

Modified enzymatic procedure for the routine determination of glycerol and triglycerides in plasma.

A modification of Wieland's enzymatic procedure for glycerol analysis is presented. It is simple and precise, and readily applicable to the routine analysis of plasma and tissue glycerol and triglycerides. Optimal precision is obtained in samples containing 0.003-0.400 micromole of glycerol per ml, which in this method is equivalent to plasma levels of 0.011 to 1.40 micromoles/ml.