The Role of Substrate on Thermal Evolution of Ag/TiO2 Nanogranular Thin Films

In multicomponent thin films, properties and functionalities related to post-deposition annealing treatments, such as thermal stability, optical absorption and surface morphology are typically rationalized, neglecting the role of the substrate. Here, we show the role of the substrate in determining the temperature dependent behaviour of a paradigmatic two-component nanogranular thin film (Ag/TiO2) deposited by gas phase supersonic cluster beam deposition (SCBD) on silica and sapphire. Up to 600 °C, no TiO2 grain growth nor crystallization is observed, likely inhibited by the Zener pinning pressure exerted by the Ag nanoparticles on the TiO2 grain boundaries. Above 600 °C, grain coalescence, formation of However, the two substrates steer the evolution of the film morphology and optical properties in two different directions. anatase and rutile phases and drastic modification of the optical absorption are observed. On silica, Ag is still present as NPs distributed into the TiO2 matrix, while on sapphire, hundreds of nm wide Ag aggregates appear on the film surface. Moreover, the silica-deposited film shows a broad absorption band in the visible range while the sapphire-deposited film becomes almost transparent for wavelengths above 380 nm. We discuss this result in terms of substrate differences in thermal conductivity, thermal expansion coefficient and Ag diffusivity. The study of the substrate role during annealing is possible since SCBD allows the synthesis of the same film independently of the substrate, and suggests new perspectives on the thermodynamics and physical exchanges between thin films and their substrates during heat treatments.

Nano-vault architecture mitigates stress in silicon-based anodes for lithium-ion batteries

Nanomaterials undergoing cyclic swelling-deswelling benefit from inner void spaces that help accommodate significant volumetric changes. Such flexibility, however, typically comes at a price of reduced mechanical stability, which leads to component deterioration and, eventually, failure. Here, we identify an optimised building block for silicon-based lithium-ion battery (LIB) anodes, fabricate it with a ligand- and effluent-free cluster beam deposition method, and investigate its robustness by atomistic computer simulations. A columnar amorphous-silicon film was grown on a tantalum-nanoparticle scaffold due to its shadowing effect. PeakForce quantitative nanomechanical mapping revealed a critical change in mechanical behaviour when columns touched forming a vaulted structure. The resulting maximisation of measured elastic modulus (~120 GPa) is ascribed to arch action, a well-known civil engineering concept. The vaulted nanostructure displays a sealed surface resistant to deformation that results in reduced electrode-electrolyte interface and increased Coulombic efficiency. More importantly, its vertical repetition in a double-layered aqueduct-like structure improves both the capacity retention and Coulombic efficiency of the LIB.

Micropatterning of Substrates for the Culture of Cell Networks by Stencil-Assisted Additive Nanofabrication

The fabrication of in vitro neuronal cell networks where cells are chemically or electrically connected to form functional circuits with useful properties is of great interest. Standard cell culture substrates provide ensembles of cells that scarcely reproduce physiological structures since their spatial organization and connectivity cannot be controlled. Supersonic Cluster Beam Deposition (SCBD) has been used as an effective additive method for the large-scale fabrication of interfaces with extracellular matrix-mimicking surface nanotopography and reproducible morphological properties for cell culture. Due to the high collimation of SCBD, it is possible to exploit stencil masks for the fabrication of patterned films and reproduce features as small as tens of micrometers. Here, we present a protocol to fabricate micropatterned cell culture substrates based on the deposition of nanostructured cluster-assembled zirconia films by stencil-assisted SCBD. The effectiveness of this approach is demonstrated by the fabrication of micrometric patterns able to confine primary astrocytes. Calcium waves propagating in the astrocyte networks are shown.

Fabrication of High-Aspect-Ratio Cylindrical Micro-Structures Based on Electroactive Ionogel/Gold Nanocomposite

We present a fabrication process to realize 3D high-aspect-ratio cylindrical micro-structures of soft ionogel/gold nanocomposites by combining replica molding and Supersonic Cluster Beam Deposition (SCBD). Cylinders’ metallic masters (0.5 mm in diameter) are used to fabricate polydimethylsiloxane (PDMS) molds, where the ionogel is casted and UV cured. The replicated ionogel cylinders (aspect ratio > 20) are subsequently metallized through SCBD to integrate nanostructured gold electrodes (150 nm thick) into the polymer. Nanocomposite thin films are characterized in terms of electrochemical properties, exhibiting large double layer capacitance (24 μF/cm2) and suitable ionic conductivity (0.05 mS/cm) for charge transport across the network. Preliminary actuation tests show that the nanocomposite is able to respond to low intensity electric fields (applied voltage from 2.5 V to 5 V), with potential applications for the development of artificial smart micro-structures with motility behavior inspired by that of natural ciliate systems.

Antimicrobial Nanostructured Coatings: A Gas Phase Deposition and Magnetron Sputtering Perspective

Counteracting the spreading of multi-drug-resistant pathogens, taking place through surface-mediated cross-contamination, is amongst the higher priorities in public health policies. For these reason an appropriate design of antimicrobial nanostructured coatings may allow to exploit different antimicrobial mechanisms pathways, to be specifically activated by tailoring the coatings composition and morphology. Furthermore, their mechanical properties are of the utmost importance in view of the antimicrobial surface durability. Indeed, the coating properties might be tuned differently according to the specific synthesis method. The present review focuses on nanoparticle based bactericidal coatings obtained via magneton-spattering and supersonic cluster beam deposition. The bacteria–NP interaction mechanisms are first reviewed, thus making clear the requirements that a nanoparticle-based film should meet in order to serve as a bactericidal coating. Paradigmatic examples of coatings, obtained by magnetron sputtering and supersonic cluster beam deposition, are discussed. The emphasis is on widening the bactericidal spectrum so as to be effective both against gram-positive and gram-negative bacteria, while ensuring a good adhesion to a variety of substrates and mechanical durability. It is discussed how this goal may be achieved combining different elements into the coating.

Stabilization of binder-free vanadium oxide-based oxygen electrodes using Pd clusters for Li–O2 batteries

A stable binder-free carbon cloth supporting V2O5-Pd clusters was synthesized through hydrothermal and gas-phase-cluster beam deposition. The as-prepared binder-free electrode showed potential application in hybrid energy storage systems.