Luisa Sciortino

Fluorescent nitrogen-rich carbon nanodots with an unexpected β-C3N4 nanocrystalline structure

Carbon nanodots are a class of nanoparticles with variable structures and compositions which exhibit a range of useful optical and photochemical properties. Since nitrogen doping is commonly used to enhance the fluorescence properties of carbon nanodots, understanding how nitrogen affects their structure, electronic properties and fluorescence mechanism is important to fully unravel their potential. Here we use a multi-technique approach to study heavily nitrogen-doped carbon dots synthesized by a simple bottom-up approach and capable of bright and color-tunable fluorescence in the visible region. These experiments reveal a new variant of optically active carbonaceous dots, that is a nanocrystal of beta carbon nitride (β-C3N4) capped by a disordered surface shell hosting a variety of polar functional groups. Because β-C3N4 is a network of sp3 carbon and sp2 nitrogen atoms, such a structure markedly contrast with the prevailing view of carbon nanodots as sp2-carbon materials. The fluorescence mechanism of these nanoparticles is thoroughly analyzed and attributed to electronic transitions within a manifold of surface states associated with nitrogen-related groups. The sizeable bandgap of the β-C3N4 nanocrystalline core has an indirect, albeit important role in favoring an efficient emission. These results have deep implications on our current understanding of optically active carbon-based nanoparticles and reveal the role of nitrogen in controlling their properties.

Crossing the boundary between face-centred cubic and hexagonal close packed: the structure of nanosized cobalt is unraveled by a model accounting for shape, size distribution and stacking faults, allowing simulation of XRD, XANES and EXAFS

The properties of nanostructured cobalt in the fields of magnetic, catalytic and biomaterials depend critically on Co close packing. This paper reports a structural analysis of nanosized cobalt based on the whole X-ray diffraction (XRD) pattern simulation allowed by the Debye equation. The underlying structural model involves statistical sequences of cobalt layers and produces simulated XRD powder patterns bearing the concurrent signatures of hexagonal and cubic close packing (h.c.p. and f.c.c.). Shape, size distribution and distance distribution between pairs of atoms are also modelled. The simulation algorithm allows straightforward fitting to experimental data and hence the quantitative assessment of the model parameters. Analysis of two samples having, respectively, h.c.p. and f.c.c. appearance is reported. Extended X-ray absorption fine-structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectra are simulated on the basis of the model, giving a tool for the interpretation of structural data complementary to XRD. The outlined structural analysis provides a rigorous structural basis for correlations with magnetic and catalytic properties and an experimental reference for ab initio modelling of these properties.

Influence of metal–support interaction on the surface structure of gold nanoclusters deposited on native SiOx/Si substrates

The structure of small gold nanoclusters (around 2.5 nm) deposited on different silica-on-silicon (SiOx/Si) substrates is investigated using several characterization techniques (AFM, XRD, EXAFS and GISAXS). The grain morphology and the surface roughness of the deposited gold cluster layers are determined by AFM. The in-plane GISAXS intensity is modelled in order to obtain information about the cluster size and the characteristic length scale of the surface roughness. The surface morphology of the deposited clusters depends on whether the native defect-rich (n-SiOx/Si) or the defect-poor substrate obtained by thermal treatment (t-SiO2/Si) is used. Gold clusters show a stronger tendency to aggregate when deposited on n-SiOx/Si, resulting in films characterized by a larger grain dimension (around 20 nm) and by a higher surface roughness (up to 5 nm). The more noticeable cluster aggregation on n-SiOx/Si substrates is explained in terms of metal-support interaction mediated by the defects located on the surface of the native silica substrate. Evidence of metal-support interaction is provided by EXAFS, demonstrating the existence of an Au-O distance for clusters deposited on n-SiOx/Si that is not found on t-SiO2/Si.

The optical blocking filter for the ATHENA wide field imager: ongoing activities towards the conceptual design

ATHENA is the L2 mission selected by ESA to pursue the science theme “Hot and Energetic Universe” (launch scheduled in 2028). One of the key instruments of ATHENA is the Wide Field Imager (WFI) which will provide imaging in the 0.1-15 keV band over a 40’x40’ large field of view, together with spectrally and time-resolved photon counting. The WFI camera, based on arrays of DEPFET active pixel sensors, is also sensitive to UV/Vis photons. Optically generated electron-hole pairs may degrade the spectral resolution as well as change the energy scale by introducing a signal offset. For this reason, the use of an X-ray transparent optical blocking filter is needed to allow the observation of all type of X-ray sources that present a UV/Visible bright counterpart. In this paper, we describe the main activities that we are carrying on for the conceptual design of the optical blocking filter, that will be mounted on the filter wheel, in order to satisfy the scientific requirements on optical load from bright UV/Vis astrophysical source, to maximize the X-ray transmission, and to withstand the severe acoustic and vibration loads foreseen during launch.

Status of the EPIC thin and medium filters on-board XMM-Newton after more than 10 years of operation I: laboratory measurements on back-up filters

After more than ten years of operation of the EPIC camera on board the X-ray observatory XMM-Newton, we have reviewed the status of its Thin and Medium filters by performing both laboratory measurements on back-up filters, and analysis of data collected in-flight. We have selected a set of Thin and Medium back-up filters among those still available in the EPIC consortium, and have started a program to investigate their status by different laboratory measurements including: UV/VIS transmission, X-ray transmission, RAMAN IR spectroscopy, X-Ray Photoelectron Spectroscopy, and Atomic Force Microscopy. We report the results of the measurements conducted up to now, and point out some lessons learned for the development and calibration programs of filters for X-ray detectors in future Astronomy missions.

Investigation by Raman Spectroscopy of the Decomposition Process of HKUST-1 upon Exposure to Air

We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF) HKUST-1 upon exposure to air moisture (  K, 70% relative humidity). The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes take place, which are related to the occurrence of the hydrolysis of Cu-O bonds. These processes induce small but detectable variations of the peak positions and intensities of the main Raman bands of the material, which can be related to Cu-Cu, Cu-O, and O-C-O stretching modes. The critical analyses of these changes have permitted us to obtain a more detailed description of the process of decomposition taking place in HKUST-1 upon interaction with moisture. Furthermore, the reported Raman data give further strong support to the recently proposed model of decomposition of HKUST-1, contributing significantly to the development of a complete picture of the properties of this considerable deleterious effect.

Active shape correction of a thin glass/plastic x-ray mirror

Optics for future X-ray telescopes will be characterized by very large aperture and focal length, and will be made of lightweight materials like glass or plastic in order to keep the total mass within acceptable limits. Optics based on thin slumped glass foils are currently in use in the NuSTAR telescope and are being developed at various institutes like INAF/OAB, aiming at improving the angular resolution to a few arcsec HEW. Another possibility would be the use of thin plastic foils, being developed at SAO and the Palermo University. Even if relevant progresses in the achieved angular resolution were recently made, a viable possibility to further improve the mirror figure would be the application of piezoelectric actuators onto the non-optical side of the mirrors. In fact, thin mirrors are prone to deform, so they require a careful integration to avoid deformations and even correct forming errors. This however offers the possibility to actively correct the residual deformation. Even if other groups are already at work on this idea, we are pursuing the concept of active integration of thin glass or plastic foils with piezoelectric patches, fed by voltages driven by the feedback provided by X-rays, in intra-focal setup at the XACT facility at INAF/OAPA. In this work, we show the preliminary simulations and the first steps taken in this project.

Manufacturing an active X-ray mirror prototype in thin glass

Adjustable mirrors equipped with piezo actuators are commonly used at synchrotron and free-electron laser (FEL) beamlines, in order to optimize their focusing properties and sometimes to shape the intensity distribution of the focal spot with the desired profile. Unlike them, X-ray mirrors for astronomy are much thinner in order to enable nesting and reduce the areal mass, and the application of piezo actuators acting normally to the surface appears much more difficult. There remains the possibility to correct the deformations using thin patches that exert a tangential strain on the rear side of the mirror: some research groups are already at work on this approach. The technique reported here relies on actively integrating thin glass foils with commercial piezoceramic patches, fed by voltages driven by the feedback provided by X-rays, while the tension signals are carried by electrodes on the back of the mirror, obtained by photolithography. Finally, the shape detection and the consequent voltage signal to be provided to the piezoelectric array will be determined by X-ray illumination in an intra-focal setup at the XACT facility. In this work, the manufacturing steps for obtaining a first active mirror prototype are described.

COMBINED HEAT AND POWER GENERATION WITH A HCPV SYSTEM AT 2000 SUNS

This work shows the development of an innovative solar CHP system for the combined production of heat and power based upon HCPV modules working at the high concentration level of 2000 suns. The solar radiation is concentrated on commercial InGaP/InGaAs/Ge triple-junction solar cells designed for intensive work. The primary optics is a rectangular off-axis parabolic mirror while a secondary optic at the focus of the parabolic mirror is glued in optical contact with the cell. Each module consist of 2 axis tracker (Alt-Alt type) with 20 multijunction cells each one integrated with an active heat sink. The cell is connected to an active heat transfer system that allows to keep the cell at a high level of electrical efficiency (ηel > 30 %), bringing the heat transfer fluid (water and glycol) up to an output temperature of 90°C. Accordingly with the experimental data collected from the first 1 kWe prototype, the total amount of extracted thermal energy is above the 50% of the harvested solar radiation. That, in addition the electrical efficiency of the system contributes to reach an overall CHP efficiency of more than the 80%.

Temperature effects on the performances of the ATHENA X-IFU thermal filters

The X-Ray Integral Field Unit (X-IFU) detector on-board ATHENA is an array of TES micro-calorimeters that will operate at ~50 mK. In the current investigated design, five thermal filters (TF) will be mounted on the cryostat shields to attenuate IR radiative load and avoid energy resolution degradation due to photon shot noise. Each filter consists of a thin polyimide film (~50 nm thick) coated with aluminum (~30 nm thick). Since the TF operate at different temperatures in the range 0.05-300 K, it is relevant to study how temperature affects their mechanical/optical performances (e.g. near edge absorption fine structures of the atomic elements in the filter material). Such results are crucial for the proper design of the filters as well as to establish the calibration program operating temperatures. We report the preliminary results of visual inspections performed on test filters of polyimide/Al at different pressure and temperature conditions, IR transmission measurements (1-15 μm) performed in the temperature range 10- 300 K, and X-ray Absorption Spectroscopy measurements (175-1650 eV) performed in the temperature range 130-300 K.