The doping of metal oxides is an interesting route to increase catalyst activity and lower activation temperatures in H2 dissociation to replace Pt in catalysts for electrochemical devices. In this process, the roles of both the matrix and dopant cations are fundamental to understanding and designing more efficient catalysts. In this work, we have investigated the reduction process in pure and doped CeO2 films. We followed the oxidation states of Ce and dopants (Cu and Fe) during H2 exposure at ambient pressure by combining X-ray absorption spectroscopy and gas chromatography on 5 nm films in the temperature range of 300–620 K. We have observed that Cu doping (at concentrations of 5 and 14 at. %) promotes the ceria reduction, while the addition of Fe seems to have a limited impact on the oxide chemical reactivity only at low temperatures. Moreover, thanks to the chemical sensitivity of operando X-ray absorption spectroscopy, we were able to follow simultaneously the evolution of Ce and Cu oxidation states during the reaction, which has permitted to identify two distinct reduction processes taking place above and below 500 K. These measurements show that at low temperatures, the H2 dissociation takes place at the Cu1+ sites, thus explaining the higher reactivity of the Cu-doped samples. The described mechanism can help in the design of Pt-free catalysts with enhanced performances.
Infrared scattering-type scanning near-field optical microscopy (IR s-SNOM) and imaging is here exploited together with attenuated total reflection (ATR) IR imaging and scanning electron microscopy (SEM) to depict the chemical composition of fibers in hybrid electrospun meshes. The focus is on a recently developed bio-hybrid material for vascular tissue engineering applications, named Silkothane®, obtained in the form of nanofibrous matrices from the processing of a silk fibroin-polyurethane (SFPU) blend via electrospinning. Morphology and chemistry of single fibers, at both surface and subsurface level, have been successfully characterized with nanoscale resolution, taking advantage of the IR s-SNOM capability to portray the nanoscale depth profile of this modern material working at diverse harmonics of the signal. The applied methodology allowed to describe the superficial characteristics of the mesh up to a depth of about 100 nm, showing that SF and PU do not tend to co-aggregate to form hybrid fibers, at least at the length scale of hundreds of nanometers, and that subdomains other than the fibrillar ones can be present. More generally, in the present contribution, the depth profiling capabilities of IR s-SNOM, so far theoretically predicted and experimentally proven only on model systems, have been corroborated on a real material in its natural conditions with respect to production, opening the room for the exploitation of IR s-SNOM as valuable technique to support the production and the engineering of nanostructured materials by the precise understanding of their chemistry at the interface with the environment.
VO2 is one of the most studied vanadium oxides because it undergoes a reversible metal-insulator transition (MIT) upon heating with a critical temperature of around 340 K. One of the most overlooked aspects of VO2 is the band’s anisotropy in the metallic phase when the Fermi level is crossed by two bands: π* and d||. They are oriented perpendicularly in one respect to the other, hence generating anisotropy. One of the parameters tuning MIT properties is the unbalance of the electron population of π* and d|| bands that arise from their different energy position with respect to the Fermi level. In systems with reduced dimensionality, the electron population disproportion is different with respect to the bulk leading to a different anisotropy. Investigating such a system with a band-selective spectroscopic tool is mandatory. In this manuscript, we show the results of the investigation of a single crystalline 8 nm VO2/TiO2(101) film. We report on the effectiveness of linearly polarized resonant photoemission (ResPES) as a band-selective technique probing the intrinsic anisotropy of VO2.
It is well-known that all the phases of the manufacturing influence the extraordinary aesthetic and acoustic features of Stradivari’s instruments. However, these masterpieces still keep some of their secrets hidden by the lack of documentary evidence. In particular, there is not a general consensus on the use of a protein-based ground coating directly spread on the wood surface by the Cremonese Master. The present work demonstrates that infrared scattering-type scanning near-fields optical microscopy (s-SNOM) may provide unprecedented information on very complex cross-sectioned microsamples collected from two of Stradivari’s violins, nanoresolved chemical sensitivity being the turning point for detecting minute traces of a specific compound, namely proteins, hidden by the matrix when macro or micro sampling approaches are exploited. This nanoresolved chemical-sensitive technique contributed new and robust evidence to the long-debated question about the use of proteinaceous materials by Stradivari.
We grew Sr1-xLaxCuO2 thin films and SrCuO2/Sr0.9La0.1CuO2/SrCuO2 trilayers by reflection high-energy diffraction-calibrated layer-by-layer molecular beam epitaxy, to study their electrical transport properties as a function of the doping and thickness of the central Sr0.9La0.1CuO2 layer. For the trilayer samples, as already observed in underdoped SLCO films, the electrical resistivity versus temperature curves as a function of the central layer thickness show, for thicknesses thinner than 20 unit cells, sudden upturns in the low temperature range with the possibility for identifying, in the normal state, the T* and a T** temperatures, respectively, separating high-temperature linear behavior and low-temperature quadratic dependence. By plotting the T* and T** values as a function of TConset for both the thin films and the trilayers, the data fall on the same curves. This result suggests that, for the investigated trilayers, the superconducting critical temperature is the important parameter able to describe the normal state properties and that, in the limit of very thin central layers, such properties are mainly influenced by the modification of the energy band structure and not by interface-related disorder.
Hybridization of electronic states and orbital symmetry in transition metal oxides are generally considered key ingredients in the description of both their electronic and magnetic properties. In the prototypical case of La0.65Sr0.35MnO3 (LSMO), a landmark system for spintronics applications, a description based solely on Mn 3d and O 2p electronic states is reductive. We thus analyzed elemental and orbital distributions in the LSMO valence band through a comparison between density functional theory calculations and experimental photoelectron spectra in a photon energy range from soft to hard x rays. We reveal a number of hidden contributions, arising specifically from La 5p, Mn 4s, and O 2s orbitals, considered negligible in previous analyses; our results demonstrate that all these contributions are significant for a correct description of the valence band of LSMO and of transition metal oxides in general.
The growing demand for innovative means in biomedical, therapeutic and diagnostic sciences has led to the development of nanomedicine. In this context, naturally occurring tubular nanostructures composed of rolled sheets of alumino-silicates, known as halloysite nanotubes, have found wide application. Halloysite nanotubes indeed have surface properties that favor the selective loading of biomolecules. Here, we present the first, to our knowledge, structural study of DNA-decorated halloysite nanotubes, carried out with nanometric spatially-resolved infrared spectroscopy. Single nanotube absorption measurements indicate a partial covering of halloysite by DNA molecules, which show significant structural modifications taking place upon loading. The present study highlights the constraints for the use of nanostructured clays as DNA carriers and demonstrates the power of super-resolved infrared spectroscopy as an effective and versatile tool for the evaluation of immobilization processes in the context of drug delivery and gene transfer.
Perovskite-based heterostructures have recently gained remarkable interest, thanks to atomic-scale precision engineering. These systems are very susceptible to small variations of control parameters, such as two-dimensionality, strain, lattice polarizability, and doping. Focusing on the rare-earth nickelate diagram, LaNiO3 (LNO) catches the eye, being the only nickelate that does not undergo a metal-to-insulator transition (MIT). Therefore, the ground state of LNO has been studied in several theoretical and experimental papers. Here, we show by means of infrared spectroscopy that an MIT can be driven by dimensionality control in ultrathin LNO films when the number of unit cells drops to 2. Such a dimensionality tuning can eventually be tailored when a physically implemented monolayer in the ultrathin films is replaced by a digital single layer embedded in the Ruddlesden–Popper Lan+1NinO3n+1 series. We provide spectroscopic evidence that the dimensionality-induced MIT in Ruddlesden–Popper nickelates strongly resembles that of ultrathin LNO films. Our results can pave the way to the employment of Ruddlesden–Popper Lan+1NinO3n+1 to tune the electronic properties of LNO through dimensional transition without the need of physically changing the number of unit cells in thin films.
The study of ionic materials on nanometer scale is of great relevance for efficient miniaturized devices for energy applications. The epitaxial growth of thin films can be a valid route to tune the properties of the materials and thus obtain new degrees of freedom in materials design. High crystal quality SmxCe1-xO2-δ films are here reported at high doping level up to x=0.4, thanks to the good lat-tice matching with the (110) oriented NdGaO3 substrate. X-ray diffraction and transmission electron microscopy demonstrate the ordered structural quality and absence of Sm segregation at macroscopic and atomic level, respectively. Therefore, in epitaxial thin films the homogeneous doping can be obtained even with high dopant content not always approachable in bulk form, getting even an improvement of the structural properties. In situ spectroscopic measurements by x-ray photoemission and x-ray absorption show the O 2p band shift towards the Fermi level which can favor the oxygen exchange and vacancy formation on the surface when the Sm doping is increased to x=0.4. X-ray absorption spectroscopy also confirms the absence of ordered oxygen vacancy clusters and further reveals that the 5d eg and t2g states are well separated by the crystal field in the undistorted local structure even in the case of high doping level x=0.4.
Out-of-plane Ga2Se3 nanowires are grown by molecular beam epitaxy via Au-assisted heterovalent exchange reaction on GaAs substrates in the absence of Ga deposition. It is shown that at a suitable temperature around 560 degrees C the Audecorated GaAs substrate releases Ga atoms, which react with the incoming Se and feed the nanowire growth. The nanowire composition, crystal structure, and morphology are characterized by Raman spectroscopy and electron microscopy. The growth mechanism is investigated by X-ray photoelectron spectroscopy. We explore the growth parameter window and find an interesting effect of shortening of the nanowires after a certain maximum length. The nanowire growth is described within a diffusion transport model, which explains the nonmonotonic behavior of the nanowire length versus the growth parameters. Nanowire shortening is explained by the blocking of Ga supply from the GaAs substrate by thick, in-plane worm-like Ga2Se3 structures, which grow concomitantly with the nanowires, followed by backward diffusion of Ga atoms from the nanowires down to the substrate surface.
Transparent conductive oxides are a class of materials that combine high optical transparency with high electrical conductivity. This property makes them uniquely appealing as transparent conductive electrodes in solar cells and interesting for optoelectronic and infrared-plasmonic applications. One of the new challenges that researchers and engineers are facing is merging optical and electrical control in a single device for developing next-generation photovoltaic, optoelectronic devices and energy-efficient solid-state lighting. In this work, the authors investigated the possible variations in the dielectric properties of aluminum-doped ZnO (AZO) upon gating by means of spectroscopic ellipsometry (SE). The authors investigated the electrical-bias-dependent optical response of thin AZO films fabricated by magnetron sputtering within a parallel-plane capacitor configuration. The authors address the possibility to control their optical and electric performances by applying bias, monitoring the effect of charge injection/depletion in the AZO layer by means of in operando SE versus applied gate voltage.
The design and characterization of a HHG source conceived for Time and Angle Resolved PhotoElectron Spectroscopy (TR-ARPES) experiments are presented. The harmonics are selected through a grating monochromator with an innovative design able to provide XUV radiation for two distinct TR-ARPES setups.
The knowledge of the picosecond dynamics of the energy level alignment between donor and acceptor materials in organic photovoltaic devices under working conditions is a challenge for fundamental material research. We measured by means of time-resolved Resonant X-ray Photoemission Spectroscopy (RPES) the energy level alignment in ZnPc/C60 films. We employed 800 nm femtosecond laser pulses to pump the system simulating sunlight excitation and X-rays from the synchrotron as a probe. We measured changes in the valence bands due to pump induced modifications of the interface dipole. Our measurements prove the feasibility of time-resolved RPES with high repetition rate sources.
The role of trivalent rare-earth dopants on the cerium oxidation state has been systematically studied by in situ photoemission spectroscopy with synchrotron radiation for 10 mol % rare-earth doped epitaxial ceria films. It was found that dopant rare-earths with smaller ionic radius foster the formation of Ce3+ by releasing the stress strength induced by the cation substitution. With a decrease of the dopant ionic radius from La3+ to Yb3+, the out-of-plane axis parameter of the crystal lattice decreases without introducing macroscopic defects. The high crystal quality of our films allowed us to comparatively study both the ionic conductivity and surface reactivity ruling out the influence of structural defects. The measured increase in the activation energy of films and their enhanced surface reactivity can be explained in terms of the dopant ionic radius effects on the Ce4+ → Ce3+ reduction as a result of lattice relaxation. Such findings open new perspectives in designing ceria-based materials with tailored properties by choosing suitable cation substitution.
This thesis completes my work as doctoral student of the Scuola di Dottorato in Fisica, Astrofisica e Fisica Applicata at the Università degli Studi di Milano that has been carried out, starting in November 4236, mostly at the Laboratorio TASC of IOM-CNR3 in the premises of the Elettra - Sincrotrone Trieste and FERMI@Elettra infrastructures4, in the framework of the NFFA and APE-beamline facilites5, as well as by accessing international large scale infrastructures and laboratories. The activity has addressed the development of experimental methodologies and novel instrumentation oriented to the study of the dynamical properties of highly correlated materials after high energy excitation. The science programme has been carried out by exploiting ultrafast femtosecond probes from the optical regime (Ti-Sa lasers, fibre laser oscillators) to the extreme UV-soft X rays at FERMI, to the picosecond hard X-rays from the SPring-: and Diamond synchrotron radiation source. The sample synthesis of correlated oxides and its characterization has been performed within the NFFA facility and APE-group collaboration in Trieste as well as the design and construction of the all new laser High Harmonic Generation beam line NFFA-SPRINT and its end station for time resolved vectorial electron spin polarimetry.
Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the “bulk” ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange “surface” reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications.
This thesis reports on the construction and commissioning tests of the novel experimental set-up needed for a long term research project, named ULTRASPIN, aiming at establishing time resolved spin-resolved photoemission measurements with ultra-short (10−14 s) photon pulses from Free Electron Laser beamlines or from table-top UV/Soft-X beamlines.
The ULTRASPIN project started in the summer 2013, building on competences and instrumentation in part available from the APE-beamline group of IOM-CNR at Elettra, and with the partial support of an European contract (EXSTASY-EXperimental STation for the Analysis of the Spin Dynamics, Grant agreement N.PIIF-GA-2012-326641) and related fellowship of a world-expert of Mott scattering.
I have been involved from the beginning in the final design, in the construction and commissioning of a novel stray-field free UHV apparatus for preparing and hosting atomically clean surfaces and for measuring the spin-polarization of the photo-emitted electrons with “single pulse” sensitivity down to the 10−14 s time scale, as well as in the standard high frequency spectroscopy mode. In the commissioning phase I have participated to test experiments on ULTRASPIN as well as to relevant experiments conducted in other apparatuses.