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Auxetics are materials characterized by a negative Poisson’s ratio (NPR), an uncommon mechanical behavior corresponding to a transversal deformation tendency opposite to the traditional materials. Here we present the first example of a 3D synthetic molecular auxetic polymer, obtained by embedding a conformationally expandable cavitand as crosslinker into a rigid polymer of intrinsic microporosity (PIM). The rigidity and microporosity of the polymeric matrix are pivotal to maximize the expansion effect of the cavitand that, under mechanical stress, can assume two different conformations: a compact vase one and an extended kite form. The auxetic behavior and the corresponding NPR of the proposed material is predicted by a specific micromechanical model that considers the cavitand volume expansion ratio, the fraction of the cavitand crosslinker in the polymer, and the mechanical characteristics of the polymer backbone. The reversible auxetic behavior of the material is experimentally verified via Digital Image Correlation technique (DIC) performed during the mechanical tests on films obtained by blending the auxetic crosslinked polymer with pristine PIM. Two specific control experiments prove that the mechanically driven conformational expansion of the cavitand crosslinker is the sole responsible of the observed NPR of the polymer.

The development of new materials based on abundant elements, reduced toxicity is today crucial for the next generation of energy device. Titanium-doped hydroxyapatite (TiHA) was tested for the first time as photoanode material for Dye – Sensitized Solar Cells (DSSCs). The chemical composition and energy structure of TiHA powders with increasing titanium content (5 wt%, 10 wt% and 15 wt%) were extensively characterized by surface electron spectroscopies, XPS and UPS. Their compatibility with conventional ruthenium-based dyes molecules was also assessed, producing considerable uptake. TiHA films were produced by screen-printing technique and XRD analyses confirm the presence of apatitic structure. The film properties were completely determined by optical, morphological (FE–SEM) and functional characterizations. Finally, TiHA-based DSSCs were assembled and their photovoltaic performance were assessed. The best efficiency, equal to 0.14%, was obtained for the TiHA containing 15 wt% of titanium. These results open the path for the possible application of doped hydroxyapatite as novel materials for energy conversion systems.

Thermal exfoliation of graphite oxide is a scalable way to produce macroscopic amount of defective graphene-based compounds with high specific surface area, ideal as electrode materials in high-performance electrochemical supercapacitors. In order to increase the stored energy, defective graphene has been decorated with Ni nanoparticles without exposing the system to air. During the first charge cycle in an aqueous electrolyte (KOH 3.5M), Ni anchored to graphene proved to easily convert to Ni(OH)2 at the nanoscale and hence to reversibly assume Ni2+ and Ni3+ valence during cyclic voltammetry, through its conversion to NiOOH. Such reversible faradaic mechanism led to a one order of magnitude increase of the specific capacitance of electrodes, reaching up to 1900 F/g at 2 mV/s in KOH 3.5M. An asymmetric supercapacitor was obtained by coupling a pure graphene negative electrode with a Ni decorated graphene positive one. The supercapacitor, operating with aqueous electrolyte, was successfully cycled in the 0-1.5 V voltage range, reaching a maximum specific energy of 37 Wh/kg and a maximum specific power of 5 kW/kg. The devices displayed good reversibility and retained 72 % of the specific energy over 10 thousand of cycles. Such promising results disclose to possible industrial implementation of graphene-based supercapacitors, for a wide range of energetic application.

Titanium surface characteristics, including microtopography, chemical composition, and wettability, are essential features to achieve osseointegration of dental implants, but the choice of a particular surface topography is still a debated topic among clinicians. An increased level of implant surface hydrophilicity has been demonstrated to ameliorate osseointegration and shorten healing times. The aim of this work is to develop and test a suitable thermal-based method to enhance titanium surface wettability without modifying other characteristics of the implant surface. For this function, titanium discs with different surface topography have been thermally treated by testing different temperatures and excluding those that led to evident chromatic and morphological modifications. The selected surface gain in wettability after the treatment was assessed through contact angle measurement, chemistry modifications through x-ray photoelectron spectroscopy (XPS) analysis, and microtopography through scanning electron microscopy (SEM). Results showed a great enhancement in hydrophilicity on the tested surfaces without any other modification in terms of surface chemical composition and topography. A possible limitation of this method could be the persistent, although relatively slow, biological aging of the surfaces after the treatment. The present findings indicate that the described treatment could be a safe and effective method to enhance dental titanium hydrophilicity and thus its biological performance.

Metal oxide thin films show promising resistive switching properties, making them materials of reference for the development of memristive devices. TiO2 is probably one of the most studied materials and is being synthesized using various techniques, each of them having specific optimizable characteristics. In this paper, we report on an innovative approach by combining the sol–gel and the pulsed microplasma cluster source (PMCS) methods, exploiting the low temperature and low cost of the former process and precise control over nanocristallinity of the latter. We show that this approach overcomes the reported limitations that each technique shows in fabricating memristive devices when independently used. A side-by-side comparison of the TiO2 thin films produced by the PMCS, sol–gel, and PMCS/sol–gel hybrid methods (HM) demonstrates an improvement of the memristive properties and a reduction of the electrical shorts in the TiO2 based devices.

A novel colorimetric nanosensor is reported for the selective and sensitive determination of cysteine using magnetic-sulfur, nitrogen graphene quantum dots (Fe3O4/S, N-GQDs), and gold nanoparticles (Au NPs). Thus, S, N-GQDs was firstly immobilized on Fe3O4 nanoparticles through its magnetization in the presence of Fe3+ in the alkali solution. The prepared Fe3O4/S, N-GQDs were dispersed in cysteine solution resulting in its quick adsorption on the surface of the Fe3O4/S, N-GQDs through hydrogen bonding interaction. Then, Au NPs solution was added to this mixture that after a short time, the color of Au NPs changed from red to blue, the intensity of surface plasmon resonance peak of Au NPs at 530 nm decreased, and a new peak at a higher wavelength of 680 nm appeared. The effective parameters on cysteine quantification were optimized via response surface methodology using the central composite design. Under optimum conditions, the absorbance ratio (A680/A530) has a linear proportionality with cysteine concentration in the range of 0.04–1.20 μmol L−1 with a limit of detection of 0.009 μmol L−1. The fabrication of the reported nanosensor is simple, fast, and is capable of efficient quantification of ultra traces of cysteine in human serum and urine real samples.

Graphene-based miniaturized supercapacitors, obtained via laser conversion of suitable precursors, have been attracting recent attention for the production of energy storage small-scale devices. In this work, a one-pot synthesis of TiO2 nanoparticles embedded in porous graphene-based electrodes has been obtained with the LightScribe® technology, by converting the precursor materials through the absorption of a DVD burner infrared laser light. Enhanced electrochemical performance of devices has been achieved thanks to the combination of faradic surface reactions, arising from metal oxide nanoparticles, with the conventional electrochemical double layer capacitance, arising from porous graphene. Micro-supercapacitors, consisting of TiO2-graphene electrodes, have been tested by investigating two hydrogel polymer electrolytes, based on polyvinyl alcohol/H3PO4 and polyvinyl alcohol/H2SO4, respectively. Specific areal capacitance up to 9.9 mF/cm2 are obtained in TiO2-graphene devices, corresponding to a volumetric capacitance of 13 F/cm3 and doubling the pristine graphene-based device results. The micro-supercapacitors achieved specific areal energy and specific areal power of 0.22 μWh/cm2 and 39 μW/cm2, along with a cyclability greater than 3000 cycles. These high-performance results suggest laser-scribed TiO2-graphene nanostructures as remarkable candidates in micro-supercapacitors for environment-friendly, large-scale and low-cost applications.

Two-dimensional transition metal dichalcogenides (TMDs) represent an ideal testbench for the search of materials by design, because their optoelectronic properties can be manipulated through surface engineering and molecular functionalization. However, the impact of molecules on intrinsic physical properties of TMDs, such as superconductivity, remains largely unexplored. In this work, the critical temperature (TC) of large-area NbSe2 monolayers is manipulated, employing ultrathin molecular adlayers. Spectroscopic evidence indicates that aligned molecular dipoles within the self-assembled layers act as a fixed gate terminal, collectively generating a macroscopic electrostatic field on NbSe2. This results in an ∼55% increase and a 70% decrease in TC depending on the electric field polarity, which is controlled via molecular selection. The reported functionalization, which improves the air stability of NbSe2, is efficient, practical, up-scalable, and suited to functionalize large-area TMDs. Our results indicate the potential of hybrid 2D materials as a novel platform for tunable superconductivity., This work was supported by the European Union H2020 under the Marie Sklodowska-Curie Actions (766025-QuESTech and 748971-SUPER2D) and by the ERC Starting Grant LINKSPM (Grant 758558), by “la Caixa” Foundation (ID 100010434), under the agreement LCF/BQ/PI19/11690017 and by the Spanish MICINN under the Maria de Maeztu Units of Excellence Programme (MDM-2016-0618), Project No. MAT2015-65159-R, MAT2017-88377-C2-1-R, RTI2018-094861-B-100 and PID2019-108153GA-I00.

Two-dimensional transition metal dichalcogenides (TMDs) represent an ideal testbench for the search of materials by design, because their optoelectronic properties can be manipulated through surface engineering and molecular functionalization. However, the impact of molecules on intrinsic physical properties of TMDs, such as superconductivity, remains largely unexplored. In this work, the critical temperature (

A study leading to the development of a piezoelectric sensing device for environmental monitoring of aromatic micropollutants in water is reported. A Piezoelectric Quartz Crystal (PQC) was functionalized through electropolymerization of a quinoxaline cavitand, known to possess remarkable capabilities in selectively trapping aromatic compounds through multiple π-π and CH-π interactions. The obtained film was characterized via X-ray Photoelectron spectroscopy (XPS) to elucidate its chemical composition. The design and synthesis of the new quinoxaline cavitand functionalized at the upper rim with a bithiophene moiety suitable for electropolymerization is described. The molecular structure of the new receptor was elucidated via X-ray diffraction analysis. The performance of the obtained sensor towards selected chlorinated and not chlorinated hydrocarbons in water was tested. Excellent limit of detection (0.17 ppm), below the present stringent Italian value, was achieved for 1,2,4-trichlorobenzene, outperforming conventional systems. The frequencymetric sensor showed high reproducibility from independent functionalized PQCs, with RSD values lower than 5%.

Here were report a study of picene nano-cristalline thin films doped with pentacene molecules. The thin films were grown by supersonic molecular beam deposition with a doping concentration that ranges between less than one molecules of pentacene every 104 picene molecules up to about one molecule of pentacene every 102 of picene. Morphology and opto-electronic properties of the films were studied as a function of the concentration of dopants. The optical response of the picene films, characterized by absorption, steady-state and time-resolved photoluminescence measurements, changes dramatically after the doping with pentacene. An efficient energy transfer from the picene host matrix to the pentacene guest molecules was observed giving rise to an intense photoluminescence coming out from pentacene. This efficient mechanism opens the possibility to exploit applications where the excitonic states of the guest component, pentacene, are of major interest such as MASER. The observed mechanism could also serve as prototypical system for the study of the photophysics of host guest systems based on different phenacenes and acenes., Comment: 15 pages, 6 figures

We report a comprehensive study of the biocompatibility and neurocompatibility of titanium dioxide films (TiO2) prepared by Pulsed Microplasma Cluster Source (PMCS). This technique uses supersonic pulsed beams seeded by clusters of the metal oxide synthesized in a plasma discharge. The final stoichiometry of the TiO2 thin films is tuned changing the gas mixture, achieving stoichiometric or oxygen overstoichiometric films. All the films showed consistent biocompatibility and a spontaneous absorption of poly-d-lysine (PDL) that favors the adhesion and growth of murine cortical neurons. Moreover, the bioelectrical activity of the neuronal culture grown on the TiO2 film can be modulated by changing the chemistry of the surface. This work paves the way to develop a bio-hybrid neuromorphic device, where viable nerve cells are grown directly over a titanium dioxide film showing a network of memristors.

Having single atoms or small clusters docked onto a single layer graphene represents a charming feature for energy-storage and catalysis. Unfortunately, the large cohesion energy of transition metals often prevents the isolation of nanoscopic clusters, which invariably tend to aggregate. The decoration of defective graphene layers with single Pt atoms and sub-nanometric clusters is herein achieved by exploiting metal carbonyl clusters, as precursor, and investigated by means of transmission electron microscopy and X-ray photoemission spectroscopy. Unexpectedly, the process of aggregation of Pt into larger clusters is inhibited onto the surface of defective graphene, where the Pt-clusters are found to fragment even into single metal atoms.

In this study, a comprehensive investigation of the role of sulfur vacancies on the electronic structure and surface reactivity of molybdenum disulfide is presented. A 2H-MoS2 single crystal was annealed at two different temperatures, namely, 300 and 500 degrees C in vacuum, in order to generate sulfur vacancies in a controlled manner. The detailed characterization of the electronic structure by means of X-ray and ultraviolet photoelectron spectroscopy clearly evidences the formation of a strong surface dipole as well as surface band bending due to the excess of negative charge on the Mo centers, as a consequence of the generated sulfur vacancies. After thermal treatment, a mercaptoundecylphosphonic acid molecule, which consists of a thiol (S-H) tail group and a phosphonic acid group on the other end, was covalently attached on the surface through wet chemical functionalization in order to refill the sulfur vacancies. As a consequence of the vacancy refilling, the surface band bending is reversed and the surface dipole is remarkably decreased, being close to the initial value of the pristine surface.

WSe

The burden of paediatric Hepatitis C virus (HCV) infection across Europe is unknown, as are current policies regarding monitoring and treatment. This collaborative study aimed to collect aggregate data to characterise the population of = 6 years and 90% vertically infected. HCV genotype 1 was the most common (n 380; 57.3%), followed by genotype 3, 4 and 2. Seventeen children (3%) with chronic HCV infection were diagnosed with cirrhosis, and six were reported to have received liver transplantation for HCV-related liver disease. The majority (n 425; 64.1%) of the European children with HCV infection remained treatment-naive in 2016. Age affected clinicians’ attitudes towards treatment; 94% reported being willing to use direct-acting antivirals, if available, in adolescents (aged >= 11 years), 78% in children aged 6-10 and 42% in those 3-5 years of age (Pearson correlation coefficient -0.98; P 0.0001). This survey provides the largest characterisation of the population of children in clinical follow-up for chronic HCV infection in Europe, alongside important contextual information on their management and treatment. Discussion is needed around strategies and criteria for use of direct-acting antivirals in these children.

In this paper a novel approach is presented to prepare flexible and transparent conducting films, whose components can be separated and recovered via a recycling process. The fabrication method is based on low power sputtering of ultrathin gold layers on sodium alginate free-standing films. The resulting foils are thin, easy to handle, and shape, while showing good conductive properties. In particular, they show excellent resistance to mechanical stress, like bending or rubbing, and are highly stable in ambient atmosphere over several months. Therefore they may represent a very promising candidate to be employed in green electronics, thanks to the reduced energy consumption required for their fabrication, the absence of toxic components or chemicals that are derived from oil, and the possibility to disassemble the devices at the end of their life in environmentally friendly conditions.

This chapter reports the progress on the fabrication of thin film CIGS-based solar cells by means of the low temperature pulsed electron deposition technique. The innovative and multidisciplinary approach aims to solve the main issues preventing a possible industrial scale up of the process, i.e. the need of a fast, reliable and automated process, suitable for both static and dynamic deposition of CIGS solar cells on flexible substrates. The final goal is to open new opportunities, particularly in the emerging field of the building-integrated photovoltaic.

We report on the preparation of a novel hierarchically-porous super-activated carbon originating from organic waste with specific surface area exceeding 3000 m2/g, obtained starting from biochar derived by the pyrolysis of poultry litter. The chemical activation process proved to be efficient to remove the majority of impurities other than carbon, stabilizing a highly porous hierarchical structure with local graphene-like morphology. The presence of P and S with concentration below 0.1 wt% distinguishes this activated carbon from the usual ones obtained from vegetal sources. Thanks to these features, the obtained porous compound demonstrated to behave as an excellent electrode material for high-performance symmetric supercapacitors, reaching high specific capacitance up to 229 (13) F/g. Remarkably, the devices also supply high current density of 10 A/g without using any conducting additives and display high power density and reliability. Moreover, these optimal performances have been obtained operating by using simple eco-friendly electrolytes, like KOH and Na2SO4 aqueous solutions. The availability, the biocompatibility and the inexpensiveness of the starting materials, together with the low environmental impact of the electrolyte, suggest possible large-scale applications for such devices, for example in the field of transportation or in renewable energy-grids, but also in the field of bio-medicine.

Robust cell adhesion is known to be necessary to promote cell colonization of biomaterials and differentiation of progenitors. In this paper, we propose the functionalization of Silicon Oxycarbide (SiOxCy) nanowires (NWs) with 3-mercaptopropyltrimethoxysilane (MPTMS), a molecule containing a terminal –SH group. The aim of this functionalization was to develop a surface capable to adsorb proteins and promote cell adhesion, proliferation and a better deposition of extracellular matrix. This functionalization can be used to anchor other structures such as nanoparticles, proteins or aptamers. It was observed that surface functionalization markedly affected the pattern of protein adsorption, as well as the in vitro proliferation of murine osteoblastic cells MC3T3-E1, which was increased on functionalized nanowires (MPTMS-NWs) compared to bare NWs (control) (p

In this work we propose a realistic model of nanometer-thick SiC/SiOx core/shell nanowires (NWs) using a combined first-principles and experimental approach. SiC/SiOx core/shell NWs were first synthesised by a low-cost carbothermal method and their chemical-physical experimental analysis was accomplished by recording X-ray absorption near-edge spectra. In particular, the K-edge absorption lineshapes of C, O, and Si are used to validate our computational model of the SiC/SiOx core/shell NW architectures, obtained by a multiscale approach, including molecular dynamics, tight-binding and density functional simulations. Moreover, we present ab initio calculations of the electronic structure of hydrogenated SiC and SiC/SiOx core/shell NWs, studying the modification induced by several different substitutional defects and impurities into both the surface and the interfacial region between the SiC core and the SiOx shell. We find that on the one hand the electron quantum confinement results in a broadening of the band gap, while hydroxyl surface terminations decrease it. This computational investigation shows that our model of SiC/SiOx core/shell NWs is capable to deliver an accurate interpretation of the recorded X-ray absorption near-edge spectra and proves to be a valuable tool towards the optimal design and application of these nanosystems in actual devices.

Herein, we describe the use of soft X-ray reflectivity at the carbon K-edge to study the molecular organization (orientation, structure, and morphology) of pentacene active films in a top-contact transistor geometry. This technique is not affected by sample charging, and it can be applied in the case of insulating substrates. In addition, the sampling depth is not limited to the near-surface region, giving access to buried device interfaces (metal/organic and dielectric/organic). Spectral lineshape simulations, based on ab-initio calculations using a realistic 3D layer-by-layer model, allow us to unravel the details of the molecular organization in all the specific and crucial areas of the active film, overcoming the limitations of conventional approaches. The tilt angle of the long molecular axis in the whole film is found to progressively decrease with respect to the substrate normal from 25° to 0° with the increasing film thickness. A full vertical alignment, optimal for in-plane charge hopping, is reached only after the complete formation of the first five monolayers. Remarkably, starting from the first one in contact with the dielectric substrate, all the monolayers in the stack show a change in orientation with the increasing thickness. On the other hand, at the buried interface with a gold top-contact, the molecules assume a flat orientation that only propagates for two or three monolayers into the organic film. Top-contact devices with the highest performances can thus be obtained using films of at least ten monolayers. This explains the observed thickness dependence of charge mobility in pentacene transistors.

Transition metal dichalcogenides, such as molybdenum disulfide (MoS2), show peculiar chemical/physical properties that enable their use in applications ranging from micro- and nano-optoelectronics to surface catalysis, gas and light detection, and energy harvesting/production. One main limitation to fully harness the potential of MoS2 is given by the lack of scalable and low environmental impact synthesis of MoS2 films with high uniformity, hence setting a significant challenge for industrial applications. In this work, we develop a versatile and scalable sol-gel-derived MoS2 film fabrication by spin coating deposition of an aqueous sol on different technologically relevant, flexible substrates with annealing at low temperatures (300 °C) and without the need of sulfurization and/or supply of hydrogen as compared to cutting-edge techniques. The electronic and physical properties of the MoS2 thin films were extensively investigated by means of surface spectroscopy and structural characterization techniques. Spatially homogenous nanocrystalline 2H-MoS2 thin films were obtained exhibiting high chemical purity and excellent electronic properties such as an energy band gap of 1.35 eV in agreement with the 2H phase of the MoS2, and a density of states that corresponds to the n-type character expected for high-quality 2H-MoS2. The potential use of sol-gel-grown MoS2 as the candidate material for electronic applications was tested via electrical characterization and demonstrated via the reversible switching in resistivity typical for memristors with a measured ON-OFF ratio >=102. The obtained results highlight that the novel low-cost fabrication method has a great potential to promote the use of high-quality MoS2 in technological and industrial-relevant scalable applications. © 2018 American Chemical Society.

In this work we propose a realistic model of nanometer-thick SiC/SiO x core/shell nanowires (NWs) using a combined first-principles and experimental approach. SiC/SiO x core/shell NWs were first synthesised by a low-cost carbothermal method and their chemical-physical experimental analysis was accomplished by recording X-ray absorption near-edge spectra. In particular, the K-edge absorption lineshapes of C, O, and Si are used to validate our computational model of the SiC/SiO x core/shell NW architectures, obtained by a multiscale approach, including molecular dynamics, tight-binding and density functional simulations. Moreover, we present ab initio calculations of the electronic structure of hydrogenated SiC and SiC/SiO x core/shell NWs, studying the modification induced by several different substitutional defects and impurities into both the surface and the interfacial region between the SiC core and the SiO x shell. We find that on the one hand the electron quantum confinement results in a broadening of the band gap, while hydroxyl surface terminations decrease it. This computational investigation shows that our model of SiC/SiO x core/shell NWs is capable to deliver an accurate interpretation of the recorded X-ray absorption near-edge spectra and proves to be a valuable tool towards the optimal design and application of these nanosystems in actual devices. © 2018 The Royal Society of Chemistry.

The unoccupied electronic structure of tetrakis(phenyl)- and tetrakis(pentafluorophenyl)-porphyrin thick films deposited on SiO2/Si(100) native oxide surfaces has been thoroughly studied by combining the outcomes of near-edge X-ray absorption fine structure spectroscopy at the C, N, and F K-edges with those of scalar relativistic zeroth order regular approximation time-dependent density functional theory calculations carried out on isolated molecules. Both experimental and theoretical results concur to stress the electronic inertness of pristine porphyrin macrocycle based 1sC -> ?* and 1sN -> ?* transitions whose excitation energies are substantially unaffected upon fluorination. The obtained results complement those published by the same group about the occupied states of both molecules, thus providing the missing tile to get a thorough description of the halide decoration effects on the electronic structure of the tetrakis(phenyl)-porphyrin.

The Hummers' method for graphite oxide (GO) preparation has been applied to graphite nanoplatelets, in order to achieve higher reaction yield and faster kinetics. Aqueous GO solutions have been used to produce uniform GO films on a polyethylene terephthalate substrate, generating graphene patterns in a controlled way (widths of a few tens of microns). The reduction of GO deposited on the polymeric substrate has been performed by using a Nd:YVO4 continuous-wave frequency-duplicated laser. Spectroscopic and diffractometric characterizations (FT-IR, visible-NIR, Raman, XPS, and XRD) have shown that the reduction process induced by the laser annealing technique is mainly due to dehydration of the GO layers. It has been obtained by means of a suitable laser optical apparatus, a controlled reduction of GO without damaging the substrate, and precise writing of micro-tracks that can be used as electrically and thermally conductive patterns.

We report a comprehensive study of the biocompatibility and neurocompatibility of titanium dioxide films (TiO

We describe a procedure for the optimization of a 3C-SiC buffer layer for the deposition of 3C-SiC on (001) Si substrates. A 100 – 150 nm thick SiC buffer was deposited after a standard carbonization at 1125 °C, while increasing the temperature from 1125 °C to 1380 °C. Ramp time influenced the quality and the crystallinity of the buffer layer and the presence of voids at the SiC/Si interface. After the optimization of the buffer, to demonstrate its effectiveness, a high-quality 3C-SiC was grown, with excellent surface morphology, crystallinity and low stress.

Many efforts have been spent in the last decade for the development of nanoscale synaptic devices integrated into neuromorphic circuits, trying to emulate the behavior of natural synapses. The study of brain properties with the standard approaches based on biocompatible electrodes coupled to conventional electronics, however, presents strong limitations, which in turn could be overcame by the in-situ growth of neuronal networks coupled to memristive devices. To meet this challenging task, here two different chips were designed and fabricated for culturing neuronal cells and sensing their electrophysiological activity. The first chip was designed to be connected to an external memristor, while the second chip was coated with TiO2 films owning memristive properties. The biocompatibility of chips was preliminary analyzed by culturing the hybrid motor-neuron cell line NSC-34 and by measuring the electrical activity of cells interfacing the chip with a standard patch-clamp setup. Next, neurons were seeded on chips and their activity measured with the same setup. For both cell types total current and voltage responses were evoked and recorded with optimal results with no breakdowns. In addition, an external stimulation was applied to cells through chip electrodes, being effective and causing no damage or pitfalls to the cells. Finally, the whole bio-hybrid system, i.e. the chip interconnected with a commercial memristor, was tested with promising results. Spontaneous electrical activity of neurons grown on the chip was indeed present and this signal was collected and sent to the memristor, changing its state. Taken together, we demonstrated the ability of memristor to work with a synaptic/plastic response together with natural systems, opening the way for the further implementation of basic computing elements able to perform both storage and processing of data, as in natural neurons.

A procedure for the optimization of a 3C–SiC buffer layer for the deposition of 3C–SiC/(001) Si is described. After a standard carbonization at 1125 °C, SiH 4 and C 3 H 8 were added to the gas phase while the temperature was raised from 1125 °C to the growth temperature of 1380 °C with a controlled temperature ramp to grow a thin SiC layer. The quality and the crystallinity of the buffer layer and the presence of voids at the SiC/Si interface are related to the gas flow and to the heating ramp rate. In order to improve the buffer quality the SiH 4 and C 3 H 8 flows were changed during the heating ramp. On the optimized buffer no voids were detected and a high-quality 1.5 μm 3C–SiC was grown to demonstrate the effectiveness of the described buffer.

Singlet oxygen has attracted great attention in physical, chemical, as well as biological studies, mainly due to its high reactivity and strong oxidising properties. In this context, hybrid nanosystems comprised of (inorganic) X-ray absorbing nanostructures and (organic) light-sensitive material (photosensitizers) can potentially overcome the limitations of visible light penetration in matter. A deep investigation of the interface of such hybrid nanosystems for X-ray induced generation of singlet oxygen is key to better understand the processes at the hybrid interface, and to control the energy transfer from inorganic to organic counterparts, which ultimately leads to enhanced singlet oxygen generation. Here, we demonstrate that SiC/SiOx core/shell nanowires functionalized with the tetrakis.pentafluorophenyl) porphyrin can act as a highly promising and viable strategy to generate singlet oxygen, making this novel hybrid nanosystem attractive for applications in photocatalysis and nanomedical applications. Using different excitation sources (i. e., electrons, visible light, and X-rays) our findings prove that SiC/SiOx core/shell nanowires show X-ray excited optical luminescence, and that optical emission of the photosensitizer is largely enhanced by the nanowires, yielding an efficient energy transfer. A consequent singlet oxygen production of the functionalized nanowires is demonstrated after X-ray excitation in a clinical linear accelerator. These findings will provide an insight in developing an effective route to the molecular functionalization of SiC/SiOx core/shell nanowires and their potential use as singlet oxygen generators.

The optical band gap energy and the electronic processes involved are important parameters of a semiconductor material and it is therefore important to determine their correct values. Among the possible methods, the spectrophotometric is one of the most common. Several methods can be applied to determine the optical band gap energy and still now a defined consensus on the most suitable one has not been established. A highly diffused and accurate optical method is based on Tauc relationship, however to apply this equation is necessary to know the nature of the electronic transitions involved commonly related to the coefficient n. For this purpose, a spectrophotometric technique was used and we developed a graphical method for electronic transitions and band gap energy determination for samples in powder form. In particular, the n coefficient of Tauc equation was determined thorough mathematical elaboration of experimental results on TiO2 (anatase), ZnO, and SnO2. The results were used to calculate the band gap energy values and then compared with the information obtained by Ultraviolet Photoelectron Spectroscopy (UPS). This approach provides a quick and accurate method for band gap determination through n coefficient calculation. Moreover, this simple but reliable method can be used to evaluate the nature of electronic transition that occurs in a semiconductor material in powder form. (C) 2016 Elsevier B.V. All rights reserved.

We report the development of sol-gel derived TiO2 thin films with adjustable and defined properties suitable for memristive cell fabrication. Memristive cells were developed by the sol-gel deposition of titania onto SiO2/Ti/Pt engineered electrodes via spin coating, followed by diverse curing and annealing procedures. The influence of the processing conditions and the sol's chemical composition on the film properties, and therefore on the memristive response, was studied by micro-Raman and transmission spectroscopies, profilometry, ellipsometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray absorption and diffraction spectroscopies (XAS and XRD). A memristive response was acquired from a number of these cells, revealing a dependence of the electrical behavior on minor changes in the TiO2 structure, electroforming parameters, and architecture. Thus, these properties provide a handle for fine-tuning electrical performance.

In this work we report the enhancement of the 3C-SiC band edge luminescence induced by the SiO2 shell in SiC/SiO2 core/shell nanowires (NWs) system. We demonstrate that the shell enhances the SiC near band edge luminescence and we argue the formation of a type-I quantum well between the SiC core and the SiO2 shell, with the consequent injection of carriers from the larger band-gap shell to the narrower band-gap core.

Bulk defective graphene produced by thermal exfoliation of graphite oxide was treated under H-2 and investigated with X-ray photoemission spectroscopy, neutron spectroscopy, and solid state nuclear magnetic resonance. Graphene defects appear effective in dissociating H2 molecule and in promoting H covalent absorption on the carbon backbone. Measured generalized phonon density of states shows the presence of localized peaks ascribed to C H bending modes already in pristine graphene, whose intensities enhance when samples are treated under H2 at 1273 K. However, H-1 NMR evidences a thermally activated dynamics with a correlation time of a few microseconds assigned to a part of H atoms bound onto the graphene plane. These findings point toward a diffusive dynamics of the hydrogen chemically e, bound to graphene sheets, already active at room temperature.

High kinetic energy impacts between inorganic surfaces and molecular beams seeded by organics represent a fundamental tool in materials science, particularly when they activate chemical–physical processes leading to nanocrystals' growth. Here we demonstrate single-layer graphene synthesis on copper by C60 supersonic molecular beam (SuMBE) epitaxy. A growth temperature down to 645 °C, lower than that typical of chemical vapour deposition (1000 °C), is achieved by thermal decomposition of C60 with the possibility of further reduction. Using a variety of electron spectroscopy and microscopy techniques, and first-principles simulations, we describe the chemical–physical mechanisms activated by SuMBE and assisted by thermal processes, resulting in graphene growth. In particular, we find a role of high kinetic energy deposition in enhancing the organic/inorganic interface interaction and controlling the fullerene cage openings. These results, while discussed in the specific case of graphene on copper, are potentially extendible to different metallic or semiconductor substrates and where lower processing temperature is desirable.

Understanding the adsorption mechanisms of large molecules on metal surfaces is a demanding task. Theoretical predictions are difficult because of the large number of atoms that have to be considered in the calculations, and experiments aiming to solve the molecule-substrate interaction geometry are almost impossible with standard laboratory techniques. Here, we show that the adsorption of complex organic molecules can induce perfectly ordered nanostructuring of metal surfaces. We use surface X-ray diffraction to investigate in detail the bonding geometry of C60 with the Pt(111) surface, and to elucidate the interaction mechanism leading to the restructuring of the Pt(111) surface. The chemical interaction between one monolayer of C60 molecules and the clean Pt(111) surface results in the formation of an ordered SQR13xSQR13R13.9° reconstruction based on the creation of a surface vacancy lattice. The C60 molecules are located on top of the vacancies, and 12 covalent bonds are formed between the carbon atoms and the 6 platinum surface atoms around the vacancies. In-plane displacements induced on the platinum substrate are of the order of a few picometres in the top layer, and are undetectable in the deeper layers.

This paper reports on the preparation, surface and electrical characterisation of titanium dioxide thin-films for highly selective gas sensor devices. Seeded supersonic beam deposition technique was used to prepare nanostructured thin films for gas sensors application. Two different typologies of sensors, prepared under different deposition conditions, were investigated. They showed gas-sensing properties comparable to most of the TiO 2 films realised with other more conventional techniques.

The growth of silicon carbide (SiC), a large band-gap semiconductor, on Si is very promising for applications to sensors, electronics and optoelectronics. However, difficulties in controlling the growth of the material and the interface have inhibited the production of SiC based devices. We have developed a new technique (Supersonic Molecular Beam Epitaxy, SuMBE) for the heteroepitaxial growth of SiC on Si by means of supersonic molecular beams of fullerene (C60). The carbide synthesis can be induced by the kinetic activation of the process due to the kinetic energy released in C60–Si collision. This has made possible a reduction of the growth substrate temperature and an improvement of electronic and structural properties of the SiC film. We present a study of the processes governing the growth of very thin SiC film by C60 supersonic beam. Two films were grown in Ultra High Vacuum (UHV) on Si(111)-7×7, at substrate temperature of 800 °C, using the same fullerene beam but selecting C60 particles having different characteristics. Surface electronic and structural characterizations were done both in situ and ex situ. The results show that strongly different growth processes can be achieved by controlling the precursor kinetic energy.

We propose a multi-technique approach based on in-vacuum synthesis of metal oxides to optimize the memristive properties of devices that use a metal oxide thin film as insulating layer. Pulsed Microplasma Cluster Source (PMCS) is based on supersonic beams seeded by clusters of the metal oxide. Nanocrystalline TiO{sub 2} thin films can be grown at room temperature, controlling the oxide stoichiometry from titanium metal up to a significant oxygen excess. Pulsed Electron beam Deposition (PED) is suitable to grow crystalline thin films on large areas, a step towards producing device arrays with controlled morphology and stoichiometry. Atomic Layer Deposition (ALD) is a powerful technique to grow materials layer-by-layer, finely controlling the chemical and structural properties of the film up to thickness of 50-80 nm. We will present a few examples of metal-insulator-metal structures showing a pinched hysteresis loop in their current-voltage characteristic. The structure, stoichiometry and morphology of the metal oxide layer, either aluminum oxide or titanium dioxide, is investigated by means of scanning electron microscopy (SEM) and by Raman scattering.