Mesoporous Si and multi-layered Si/C films by Pulsed Laser Deposition as Li-ion microbattery anodes

Silicon is a very attractive Li-ion battery anode material due to its high theoretical capacity, but proper nanostructuring is needed to accommodate the large volume expansion/shrinkage upon reversible cycling. Hereby, novel mesoporous Si nanostructures are grown at room temperature by simple and rapid Pulsed Laser Deposition (PLD) directly on top of the Cu current collector surface. The samples are characterised from the structural/morphological viewpoint and their promising electrochemical behaviour demonstrated in lab-scale lithium cells. Depending on the porosity, easily tuneable by PLD, specific capacities approaching 250 μAh cm−2 are obtained. Successively, newly elaborated bicomponent silicon/carbon nanostructures are fabricated in one step by alternating PLD deposition of Si and C, thus resulting in novel multi-layered composite mesoporous films exhibiting profoundly improved performance. Alternated deposition of Si/C layers by PLD is proven to be a straightforward method to produce multi-layered anodes in one processing step. The addition of carbon and mild annealing at 400 °C stabilize the electrochemical performance of the Si based nanostructures in lab-scale lithium cells, allowing to reach very stable prolonged reversible cycling at improved specific capacity values. This opens the way to further reducing processing steps and processing time, which are key aspects when upscaling is sought

Fabrication and Characterization of Molybdenum Tips for Scanning Tunneling Microscopy and Spectroscopy

We present a method for the preparation of bulk molybdenum tips for scanning Tunneling Microscopy and Spectroscopy (STM - STS) and we assess their potential in performing high resolution imaging and local spectroscop by measurements on different single crystal surfaces in UHV, namely Au(111), Si(111)-7x7 and titanium oxide 2D ordered nanostructures supported on Au(111). The fabrication method is versatile and can be extended to other metals, e.g. cobalt

Pulsed Laser Deposition of two-dimensional ZnO nanocrystals on Au(111): Growth, surface structure and electronic properties

Two-dimensional (2D) ZnO structures have been deposited on the Au(111) surface by means of the pulsed laser deposition (PLD) technique. In situ scanning tunneling microscopy (STM) and spectroscopy (STS) measurements have been performed to characterize morphological, structural and electronic properties of 2D ZnO at the nanoscale. Starting from a sub-monolayer coverage, we investigated the growth of ZnO, identifying different atomic layers (up to the 5th). At low coverage, we observed single- and bi-layer nanocrystals, characterized by a surface moire pattern that is associated to a graphene-like ZnO structure. By increasing the coverage, we revealed a morphological change starting from the 4th layer, which was attributed to a transition toward a bulk-like structure. Investigation of the electronic properties revealed the semiconducting character of 2D ZnO. We observed a dependence of the density of states (DOS) and, in particular, of the conduction band (CB) on the ZnO thickness, with a decreasing of the CB onset energy for increasing thickness. The CB DOS of 2D ZnO shows a step-like behaviour which may be interpreted as due to a 2D quantum confinement effect in ZnO atomic layer

Interface coupling in Au-supported MoS2–WS2 heterobilayers grown by pulsed laser deposition

Van der Waals heterostructures of transition metal dichalcogenides (TMDs) are promising systems for engineering functional layered 2D materials with tailored properties. In this work, we study the growth of WS2/MoS2 and MoS2/WS2 heterobilayers by pulsed laser deposition (PLD) under ultra-high vacuum conditions. Using Au(111) as growth substrate, we investigated the heterobilayer morphology and structure at the nanoscale by in-situ scanning tunneling microscopy. Our experiments show that the heterostructure growth can be controlled with high coverage and thickness sensitivity by tuning the number of laser pulses in the PLD process. Raman spectroscopy complemented our investigation, revealing the effect of the interaction with the metallic substrate on the TMD vibrational properties and a strong interlayer coupling between the MoS2 and WS2 layers. The transfer of the heterobilayers on a silica substrate via a wet etching process shows the possibility to decouple them from the native metallic substrate and confirms that the interlayer coupling is not substrate-dependent. This work highlights the potential of the PLD technique as a method to grow TMD heterostructures, opening to new perspectives in the synthesis of complex 2D layered materials

Bulk Cr tips for scanning tunneling microscopy and spin-polarized scanning tunneling microscopy

A simple, reliable method for preparation of bulk Cr tips for Scanning Tunneling Microscopy (STM) is proposed and its potentialities in performing high-quality and high-resolution STM and Spin Polarized-STM (SP-STM) are investigated. Cr tips show atomic resolution on ordered surfaces. Contrary to what happens with conventional W tips, rest atoms of the Si(111)-7x7 reconstruction can be routinely observed, probably due to a different electronic structure of the tip apex. SP-STM measurements of the Cr(001) surface showing magnetic contrast are reported. Our results reveal that the peculiar properties of these tips can be suited in a number of STM experimental situations

Low-frequency modes in the Raman spectrum of sp-sp2 nanostructured carbon

A novel form of amorphous carbon with sp-sp2 hybridization has been recently produced by supersonic cluster beam deposition showing the presence in the film of both polyynic and cumulenic species [L. Ravagnan et al. Phys. Rev. Lett. 98, 216103 (2007)]. Here we present a in situ Raman characterization of the low frequency vibrational region (400-800 cm-1) of sp-sp2 films at different temperatures. We report the presence of two peaks at 450 cm-1 and 720 cm-1. The lower frequency peak shows an evolution with the variation of the sp content and it can be attributed, with the support of density functional theory (DFT) simulations, to bending modes of sp linear structures. The peak at 720 cm-1 does not vary with the sp content and it can be attributed to a feature in the vibrational density of states activated by the disorder of the sp2 phase.Comment: 15 pages, 5 figures, 1 tabl

Nanostructure and phase engineering of manganese oxide thin films grown by pulsed laser deposition: a Raman and XRD study

Manganese, showing stable oxidation states spanning from +2 to +7, gives rise to a variety of oxides (MnOx) whose exploitation in several technological fields, such as energy conversion and storage, catalysis, sensing, environmental and biomedical engineering, is highly promising. Nevertheless, the chemical complexity and the structural richness of MnOx – involving mixed-valence and metastable species – make the correct identification by Raman spectroscopy challenging, further complicated by the laser sensitivity, the poor Raman activity, and the conflicting literature scenario. Moreover, a careful optimization of the material in terms of phase, structure, and morphology is highly desirable in view of the final application, where a precise control over the materials properties is essential. In this work, we discuss the capability of room-temperature pulsed laser deposition (PLD), followed by post-deposition thermal treatments, to successfully grow engineered and pure MnOx thin films, whose phase and morphology at the nanoscale can be totally decoupled and independently optimized. The detailed Raman characterization of these films enabled a clear identification of specific MnOx phases and poses the basis for the rationale of the MnOx Raman spectra. Starting from the same MnO PLD target, we obtained five different MnOx phases (i.e., MnO, Mn3O4, Mn2O3, amorphous MnO2, and α-MnO2) with tailored and tunable degree of porosity and crystallinity, by modulating process parameters like the O2 deposition partial pressure (vacuum – 100 Pa), the type of substrate, and the annealing temperature (300–900 °C) and atmosphere (air/vacuum). The Raman spectroscopy reliability of the MnOx phase assignment was assessed by thoroughly investigating the impact of the exciting laser power, and it was further validated by energy-dispersive X-ray spectroscopy, X-ray photoemission spectroscopy, and X-ray diffraction, providing additional insights into the compositional properties and the crystalline structure

Preparation and optimization of TiO2 photoanodes fabricated by pulsed laser deposition for photoelectrochemical water splitting

Quasi-1D TiO2 nanostructures prepared by pulsed laser deposition (PLD) are tested as photoanodes for photoelectrochemical water splitting application and compared with TiO2 nanotube arrays prepared by anodic oxidation. PLD TiO2 films with controlled structure and morphology ranging from compact to vertically oriented or hierarchical porous nanostructures are deposited by ablating a TiO2 target with nanosecond UV laser pulses in the presence of an O2 background atmosphere at different pressures. Thermal treatments at different temperatures are used to transform the so-obtained amorphous systems into nanocrystalline structures (mainly anatase). The effect of film density and thickness is also considered by depositing different amounts of material per unit surface. The morphology and the phase composition of the samples are characterized by SEM and Raman spectroscopy, while the photoelectrochemical water splitting performances are investigated by monitoring the photocurrent generated under illumination in a three-electrode cell. Voltammetric scans and electrochemical impedance spectroscopy analysis were also used to correlate the morphology of PLD samples with their electrochemical properties and their working mechanism in the absence and presence of a light radiation. A clear correlation between structural/morphological properties and photoelectrochemical behavior is found and ideal values of the synthesis parameters are identified, which allow the identification of the optimal quasi-1D nanoporous morphology for water splitting applications. The use of sacrificial organic reagents as hole scavengers was also considered to improve the photoelectrochemical performance of the samples

What Happens to MnO2 When It Comes in Contact with Zn2+? An Electrochemical Study in Aid of Zn/MnO2-Based Rechargeable Batteries

In the science and technology of electrochemical energy storage, different allotropes of MnO2, fabricated with a variety of methods, are assembled into electrodes, playing the role of cathode or oxygen reduction reaction (ORR) electrocatalyst. Often, MnO2-based cathodes are combined with Zn anodes into different types of batteries, resulting in contact between MnO2 and its electrochemical reaction products, and Zn2+. Awareness is growing that this interaction adversely affects the functional performance of MnO2, but no definitive understanding has been reached for this issue. This study contributes, through electrochemical measurements accompanied by microscopy and Raman spectroscopy, to a better understanding of the way the electrochemical behavior of two technologically representative types of manganese dioxide - hydrothermally grown α-MnO2 and electrodeposited γ-MnO2 (EDM) - is degraded when these materials are exposed to neutral and alkaline aqueous solutions, containing Zn2+. Specifically, we highlighted different types of irreversible changes in electrochemical response, which can be interpreted with phase-formation processes. Such changes result in the deactivation of α-MnO2 as ORR electrocatalyst, and of both α-MnO2 and EDM as zinc-ion battery (ZIB) cathodes. The electroactivity of EDM for ZIB operation can be restored if Mn2+ is added to the neutral electrolyte, because a phase, active in discharge, is electrodeposited during charging