Nanometric Moiré Stripes on the Surface of Bi2Se3 Topological Insulator.

Mismatch between adjacent atomic layers in low-dimensional materials, generating moiré patterns, has recently emerged as a suitable method to tune electronic properties by inducing strong electron correlations and generating novel phenomena. Beyond graphene, van der Waals structures such as three-dimensional (3D) topological insulators (TIs) appear as ideal candidates for the study of these phenomena due to the weak coupling between layers. Here we discover and investigate the origin of 1D moiré stripes on the surface of Bi2Se3 TI thin films and nanobelts. Scanning tunneling microscopy and high-resolution transmission electron microscopy reveal a unidirectional strained top layer, in the range 14-25%, with respect to the relaxed bulk structure, which cannot be ascribed to the mismatch with the substrate lattice but rather to strain induced by a specific growth mechanism. The 1D stripes are characterized by a spatial modulation of the local density of states, which is strongly enhanced compared to the bulk system. Density functional theory calculations confirm the experimental findings, showing that the TI surface Dirac cone is preserved in the 1D moiré stripes, as expected from the topology, though with a heavily renormalized Fermi velocity that also changes between the top and valley of the stripes. The strongly enhanced density of surface states in the TI 1D moiré superstructure can be instrumental in promoting strong correlations in the topological surface states, which can be responsible for surface magnetism and topological superconductivity.

Impact of Nitrogen on the Selective Closure of Stacking Faults in 3C-SiC.

Despite the promising properties, the problem of cubic silicon carbide (3C-SiC) heteroepitaxy on silicon has not yet been resolved and its use in microelectronics is limited by the presence of extensive defects. In this paper, we used microphotoluminescence (µ-PL), molten KOH etching, and high-resolution scanning transmission electron microscopy (HRSTEM) to investigate the effect of nitrogen doping on the distribution of stacking faults (SFs) and assess how increasing dosages of nitrogen during chemical vapor deposition (CVD) growth inhibits the development of SFs. An innovative angle-resolved SEM observation approach of molten KOH-etched samples resulted in detailed statistics on the density of the different types of defects as a function of the growth thickness of 3C-SiC free-standing samples with varied levels of nitrogen doping. Moreover, we proceeded to shed light on defects revealed by a diamond-shaped pit. In the past, they were conventionally associated with dislocations (Ds) due to what happens in 4H-SiC, where the formation of pits is always linked with the presence of Ds. In this work, the supposed Ds were observed at high magnification (by HRSTEM), demonstrating that principally they are partial dislocations (PDs) that delimit an SF, whose development and propagation are suppressed by the presence of nitrogen. These results were compared with VESTA simulations, which allowed to simulate the 3C-SiC lattice to design two 3C-lattice domains delimited by different types of SFs. In addition, through previous experimental evidence, a preferential impact of nitrogen on the closure of 6H-like SFs was observed as compared to 4H-like SFs.

Effect of Nitrogen and Aluminum Doping on 3C-SiC Heteroepitaxial Layers Grown on 4° Off-Axis Si (100).

This work provides a comprehensive investigation of nitrogen and aluminum doping and its consequences for the physical properties of 3C-SiC. Free-standing 3C-SiC heteroepitaxial layers, intentionally doped with nitrogen or aluminum, were grown on Si (100) substrate with different 4° off-axis in a horizontal hot-wall chemical vapor deposition (CVD) reactor. The Si substrate was melted inside the CVD chamber, followed by the growth process. Micro-Raman, photoluminescence (PL) and stacking fault evaluation through molten KOH etching were performed on different doped samples. Then, the role of the doping and of the cut angle on the quality, density and length distribution of the stacking faults was studied, in order to estimate the influence of N and Al incorporation on the morphological and optical properties of the material. In particular, for both types of doping, it was observed that as the dopant concentration increased, the average length of the stacking faults (SFs) increased and their density decreased.

Laser-Based Synthesis of Au Nanoparticles for Optical Sensing of Glyphosate: A Preliminary Study.

Nowadays, gold nanoparticles Au nanoparticles (AuNPs) capture great interest due to their chemical stability, optical properties and biocompatibility. The success of technologies based on the use of AuNPs implies the development of simple synthesis methods allowing, also, the fine control over their properties (shape, sizes, structure). Here, we present the AuNPs fabrication by nanosecond pulsed laser ablation in citrate-solution, that has the advantage of being a simple, economic and eco-sustainable method to fabricate colloidal solutions of NPs. We characterized the stability and the absorbance of the solutions by Ultraviolet-Visible (UV-Vis) spectroscopy and the morphology of the AuNPs by Transmission Electron Microscopy. In addition, we used the AuNPs solutions as colorimetric sensor to detect the amount of glyphosate in liquid. Indeed, glyphosate is one of the most widely used herbicides which intensive use represents a risk to human health. The glyphosate presence in the colloidal AuNPs solutions determines the aggregation of the AuNPs causing the change in the color of the solution. The variation of the optical properties of the colloidal solutions versus the concentration of glyphosate is studied.

Ultrafast Carrier Relaxation Dynamics in Quantum Confined Non-Isotropic Silicon Nanostructures Synthesized by an Inductively Coupled Plasma Process.

To exploit the optoelectronic properties of silicon nanostructures (SiNS) in real devices, it is fundamental to study the ultrafast processes involving the photogenerated charges separation, migration and lifetime after the optical excitation. Ultrafast time-resolved optical measurements provide such information. In the present paper, we report on the relaxation dynamics of photogenerated charge-carriers in ultrafine SiNS synthesized by means of inductively-coupled-plasma process. The carriers' transient regime was characterized in high fluence regime by using a tunable pump photon energy and a broadband probe pulse with a photon energy ranging from 1.2 eV to 2.8 eV while varying the energy of the pump photons and their polarization. The SiNS consist of Si nanospheres and nanowires (NW) with a crystalline core embedded in a SiOx outer-shell. The NW inner core presents different typologies: long silicon nanowires (SiNW) characterized by a continuous core (with diameters between 2 nm and 15 nm and up to a few microns long), NW with disconnected fragments of SiNW (each fragment with a length down to a few nanometers), NW with a "chaplet-like" core and NW with core consisting of disconnected spherical Si nanocrystals. Most of these SiNS are asymmetric in shape. Our results reveal a photoabsorption (PA) channel for pump and probe parallel polarizations with a maximum around 2.6 eV, which can be associated to non-isotropic ultra-small SiNS and ascribed either to (i) electron absorption driven by the probe from some intermediate mid-gap states toward some empty state above the bottom of the conduction band or (ii) the Drude-like free-carrier presence induced by the direct-gap transition in the their band structure. Moreover, we pointed up the existence of a broadband and long-living photobleaching (PB) in the 1.2-2.0 eV energy range with a maximum intensity around 1.35 eV which could be associated to some oxygen related defect states present at the Si/SiOx interface. On the other hand, this wide spectral energy PB can be also due to both silicon oxide band-tail recombination and small Si nanostructure excitonic transition.

Laser Annealing of P and Al Implanted 4H-SiC Epitaxial Layers.

This work describes the development of a new method for ion implantation induced crystal damage recovery using multiple XeCl (308 nm) laser pulses with a duration of 30 ns. Experimental activity was carried on single phosphorus (P) as well as double phosphorus and aluminum (Al) implanted 4H-SiC epitaxial layers. Samples were then characterized through micro-Raman spectroscopy, Photoluminescence (PL) and Transmission Electron Microscopy (TEM) and results were compared with those coming from P implanted thermally annealed samples at 1650-1700-1750 °C for 1 h as well as P and Al implanted samples annealed at 1650 °C for 30 min. The activity outcome shows that laser annealing allows to achieve full crystal recovery in the energy density range between 0.50 and 0.60 J/cm2. Moreover, laser treated crystal shows an almost stress-free lattice with respect to thermally annealed samples that are characterized by high point and extended defects concentration. Laser annealing process, instead, allows to strongly reduce carbon vacancy (VC) concentration in the implanted area and to avoid intra-bandgap carrier recombination centres. Implanted area was almost preserved, except for some surface oxidation processes due to oxygen leakage inside the testing chamber. However, the results of this experimental activity gives way to laser annealing process viability for damage recovery and dopant activation inside the implanted area.

Ni(OH)2@Ni core-shell nanochains as low-cost high-rate performance electrode for energy storage applications.

Energy storage performances of Ni-based electrodes rely mainly on the peculiar nanomaterial design. In this work, a novel and low-cost approach to fabricate a promising core-shell battery-like electrode is presented. Ni(OH)2@Ni core-shell nanochains were obtained by an electrochemical oxidation of a 3D nanoporous Ni film grown by chemical bath deposition and thermal annealing. This innovative nanostructure demonstrated remarkable charge storage ability in terms of capacity (237 mAh g-1 at 1 A g-1) and rate capability (76% at 16 A g-1, 32% at 64 A g-1). The relationships between electrochemical properties and core-shell architecture were investigated and modelled. The high-conductivity Ni core provides low electrode resistance and excellent electron transport from Ni(OH)2 shell to the current collector, resulting in improved capacity and rate capability. The reported preparation method and unique electrochemical behaviour of Ni(OH)2@Ni core-shell nanochains show potential in many field, including hybrid supercapacitors, batteries, electrochemical (bio)sensing, gas sensing and photocatalysis.

Influence of Different Angles of File Access on Cyclic Fatigue Resistance of Reciproc and Reciproc Blue Instruments.

INTRODUCTION: The purpose of this study was to compare the cyclic fatigue of Reciproc (REC; VDW, Munich, Germany) and Reciproc blue (REB, VDW) with different angles of file access. METHODS: The cyclic fatigue resistance of 120 new REC R25 and REB R25 (REB) files was tested. Instruments were divided into 8 groups on the basis of the access angle inside the artificial canal tested (n = 15): groups 1, 2, 3, and 4 included REC tested at 0°, 10°, 20°, and 30°, respectively, and groups 5, 6, 7, and 8 consisted of REB tested at 0°, 10°, 20°, and 30°, respectively. Resistance to cyclic fatigue was determined by recording the time to fracture in a stainless steel artificial canal with a 60° curvature and a 5-mm radius using a customized testing device. Data were analyzed using 2-way analysis of variance followed by the post hoc Tukey test with a significance level of 5%. The fracture surface of fragments was examined with a scanning electron microscope. RESULTS: The cyclic fatigue of REC was reduced from each angle of insertion, whereas REB reduced its fatigue resistance when 20° or 30°access inclination was tested. REB exhibited higher cyclic fatigue than REC when the angle of file access was 0° and 10° (P < .05), whereas there was no difference between the instruments tested at 20°. REC had higher cyclic fatigue resistance than REB at 30° (P < .05). CONCLUSIONS: REB files exhibited higher cyclic fatigue resistance than REC when the access to the canal was straight or with a limited inclination.

Structural and photoluminescence properties of silicon nanowires extracted by means of a centrifugation process from plasma torch synthesized silicon nanopowder.

We report on a method for the extraction of silicon nanowires (SiNWs) from the by-product of a plasma torch based spheroidization process of silicon. This by-product is a nanopowder which consists of a mixture of SiNWs and silicon particles. By optimizing a centrifugation based process, we were able to extract substantial amounts of highly pure Si nanomaterials (mainly SiNWs and Si nanospheres (SiNSs)). While the purified SiNWs were found to have typical outer diameters in the 10-15 nm range and lengths of up to several µm, the SiNSs have external diameters in the 10-100 nm range. Interestingly, the SiNWs are found to have a thinner Si core (2-5 nm diam.) and an outer silicon oxide shell (with a typical thickness of ∼5-10 nm). High resolution transmission electron microscopy (HRTEM) observations revealed that many SiNWs have a continuous cylindrical core, whereas others feature a discontinuous core consisting of a chain of Si nanocrystals forming a sort of 'chaplet-like' structures. These plasma-torch-produced SiNWs are highly pure with no trace of any metal catalyst, suggesting that they mostly form through SiO-catalyzed growth scheme rather than from metal-catalyzed path. The extracted Si nanostructures are shown to exhibit a strong photoluminescence (PL) which is found to blue-shift from 950 to 680 nm as the core size of the Si nanostructures decreases from ∼5 to ∼3 nm. This near IR-visible PL is shown to originate from quantum confinement (QC) in Si nanostructures. Consistently, the sizes of the Si nanocrystals directly determined from HRTEM images corroborate well with those expected by QC theory.

Self-assembly of silicon nanowires studied by advanced transmission electron microscopy.

Scanning transmission electron microscopy (STEM) was successfully applied to the analysis of silicon nanowires (SiNWs) that were self-assembled during an inductively coupled plasma (ICP) process. The ICP-synthesized SiNWs were found to present a Si-SiO2 core-shell structure and length varying from ≈100 nm to 2-3 µm. The shorter SiNWs (maximum length ≈300 nm) were generally found to possess a nanoparticle at their tip. STEM energy dispersive X-ray (EDX) spectroscopy combined with electron tomography performed on these nanostructures revealed that they contain iron, clearly demonstrating that the short ICP-synthesized SiNWs grew via an iron-catalyzed vapor-liquid-solid (VLS) mechanism within the plasma reactor. Both the STEM tomography and STEM-EDX analysis contributed to gain further insight into the self-assembly process. In the long-term, this approach might be used to optimize the synthesis of VLS-grown SiNWs via ICP as a competitive technique to the well-established bottom-up approaches used for the production of thin SiNWs.

Stability of solution-processed MAPbI3 and FAPbI3 layers.

We provide a semi-empirical model based on in situ degradation measurements to predict the durability of hybrid perovskite materials under simulated thermal operation conditions. In the model, the degradation path of MAPbI3 layers is proved to follow an Arrhenius-type law. The predictive role is played by the activation energy combined with its pre-exponential factor. Our comparative study under moisture conditions with respect to vacuum and nitrogen treatments has assessed the occurrence of an intrinsic dynamic exchange of protons between the organic cations and the inorganic cage with a direct impact on the lattice stability, for which the presence of water molecules is not mandatory. This mutual interaction produces defects inside the material and volatile species, such as HI, CH3NH2 or MAI, with an associated experimental activation energy of 1.54 eV measured under vacuum conditions in dark. This value is comparable to that calculated by the density functional theory for defect generation in MAPbI3. In air, the action of water molecules reduces the activation energy for proton exchanges in dark to 0.96 eV. As an alternative solution to increase the material stability, we demonstrate that the substitution of methylammonium (MA(+)) with the formamidinium (FA(+)) cations inside the inorganic cage gives greater robustness to the overall lattice and extends the material durability due to a different interaction between the organic molecules and the inorganic cage. This definitely supports the use of FAPbI3 in applications, provided its structure can be stabilized in the dark phase at room temperature.

Torsional and Cyclic Fatigue Resistance of a New Nickel-Titanium Instrument Manufactured by Electrical Discharge Machining.

INTRODUCTION: The purpose of this study was to evaluate the torsional and cyclic fatigue resistance of the new Hyflex EDM OneFile (Coltene/Whaledent AG, Altstatten, Switzerland) manufactured by electrical discharge machining and compare the findings with the ones of Reciproc R25 (VDW, Munich, Germany) and WaveOne Primary (Dentsply Maillefer, Ballaigues, Switzerland). METHODS: One hundred-twenty new Hyflex EDM OneFile (#25/0.08), Reciproc R25, and WaveOne Primary files were used. Torque and angle of rotation at failure of new instruments (n = 20) were measured according to ISO 3630-1 for each brand. Cyclic fatigue resistance was tested measuring the number of cycles to failure in an artificial stainless steel canal with a 60° angle and a 3-mm radius of curvature. Data were analyzed using the analysis of variance test and the Student-Newman-Keuls test for multiple comparisons. The fracture surface of each fragment was examined with a scanning electron microscope. RESULTS: The cyclic fatigue of Hyflex EDM was significantly higher than the one of Reciproc R25 and WaveOne Primary (P < .05 and P < .001, respectively). Hyflex EDM showed a lower maximum torque load (P < .05) but a significantly higher angular rotation (P < .0001) to fracture than Reciproc R25 and WaveOne Primary. No significant difference was found comparing the maximum torque load, angular rotation, and cyclic fatigue of Reciproc R25 and WaveOne Primary (P > .05). CONCLUSIONS: The new Hyflex EDM instruments (controlled memory wire) have higher cyclic fatigue resistance and angle of rotation to fracture but lower torque to failure than Reciproc R25 and WaveOne Primary files (M-wire for both files).

Visible and infrared emission from Si/Ge nanowires synthesized by metal-assisted wet etching.

Multi-quantum well Si/Ge nanowires (NWs) were realized by combining molecular beam epitaxy deposition and metal-assisted wet etching, which is a low-cost technique for the synthesis of extremely dense (about 1011 cm-2) arrays of NWs with a high and controllable aspect ratio. In particular, we prepared ultrathin Si/Ge NWs having a mean diameter of about 8 nm and lengths spanning from 1.0 to 2.7 µm. NW diameter is compatible with the occurrence of quantum confinement effects and, accordingly, we observed light emission assignable to the presence of Si and Ge nanostructures. We performed a detailed study of the photoluminescence properties of the NWs, with particular attention to the excitation and de-excitation properties as a function of the temperature and of the excitation photon flux, evaluating the excitation cross section and investigating the presence of non-radiative phenomena. PACS: 61.46.Km; 78.55.-m; 78.67.Lt.

Eu3+ reduction and efficient light emission in Eu2O3 films deposited on Si substrates.

A stable Eu3+ → Eu2+ reduction is accomplished by thermal annealing in N2 ambient of Eu2O3 films deposited by magnetron sputtering on Si substrates. Transmission electron microscopy and x-ray diffraction measurements demonstrate the occurrence of a complex reactivity at the Eu2O3/Si interface, leading to the formation of Eu2+ silicates, characterized by a very strong (the measured external quantum efficiency is about 10%) and broad room temperature photoluminescence (PL) peak centered at 590 nm. This signal is much more efficient than the Eu3+ emission, mainly consisting of a sharp PL peak at 622 nm, observed in O2-annealed films, where the presence of a SiO2 layer at the Eu2O3/Si interface prevents Eu2+ formation.

CdSe/CdS/ZnS double shell nanorods with high photoluminescence efficiency and their exploitation as biolabeling probes.

We report the synthesis, the structural and optical characterization of CdSe/CdS/ZnS "double shell" nanorods and their exploitation in cell labeling experiments. To synthesize such nanorods, first "dot-in-a-rod" CdSe(dot)/CdS(rod) core/shell nanocrystals were prepared. Then a ZnS shell was grown epitaxially over these CdSe/CdS nanorods, which led to a fluorescence quantum yield of the final core-shell-shell nanorods that could be as high as 75%. The quantum efficiency was correlated with the aspect ratio of the nanorods and with the thickness of the ZnS shell around the starting CdSe/CdS rods, which varied from 1 to 4 monolayers (as supported by a combination of X-ray diffraction, elemental analysis with inductively coupled plasma atomic emission spectroscopy and high resolution transmission electron microscopy analysis). Pump-probe and time-resolved photoluminescence measurements confirmed the reduction of trapping at CdS surface due to the presence of the ZnS shell, which resulted in more efficient photoluminescence. These double shell nanorods have potential applications as fluorescent biological labels, as we found that they are brighter in cell imaging as compared to the starting CdSe/CdS nanorods and to the CdSe/ZnS quantum dots, therefore a lower amount of material is required to label the cells. Concerning their cytotoxicity, according to the MTT assay, the double shell nanorods were less toxic than the starting core/shell nanorods and than the CdSe/ZnS quantum dots, although the latter still exhibited a lower intracellular toxicity than both nanorod samples.

Mechanism of boron diffusion in amorphous silicon.

We have elucidated the mechanism for B migration in the amorphous (a-) Si network. B diffusivity in a-Si is much higher than in crystalline Si; it is transient and increases with B concentration up to 2 x 10(20) B/cm(3). At higher density, B atoms in a-Si quickly precipitate. B diffusion is indirect, mediated by dangling bonds (DB) present in a-Si. The density of DB is enhanced by B accommodation in the a-Si network and decreases because of a-Si relaxation. Accurate data simulations allow one to extract the DB diffusivity, whose activation energy is 2.6 eV. Implications of these results are discussed.