Dual wavelength excitation for the time-resolved photoluminescence imaging of painted ancient Egyptian objects

Background: The scientific imaging of works of art is crucial for the assessment of the presence and distribution of pigments and other materials on surfaces. It is known that some ancient pigments are luminescent: these include pink red-lakes and the blue and purple pigments Egyptian Blue (CaCuSi4O10), Han blue (BaCuSi4O10) and Han purple (BaCuSi2O6). Indeed, the unique near-infrared luminescence emission of Egyptian blue allows the imaging of its distribution on surfaces. Results: We focus on the imaging of the time-resolved photoluminescence of ancient Egyptian objects in the Burri Collection from the Civic Museum of Crema and of the Cremasco (Italy). Time-resolved photoluminescence images have been acquired using excitation at 355 nm for detecting the ns-emission of red lakes and binding media; by employing 532 nm excitation Egyptian blue is probed, and the spatial distribution of its long-lived microsecond emission is imaged. For the first time we provide data on the photoluminescence lifetime of Egyptian blue directly from objects. Moreover, we demonstrate that the use of a pulsed laser emitting at two different wavelengths increases the effectiveness of the lifetime imaging technique for mapping the presence of emissions from pigments on painted surfaces. Laser-induced luminescence spectra from different areas of the objects and traditional digital imaging, using led-based lamps, long pass filters and a commercial photographic camera, complement the results from photoluminescence lifetime imaging. We demonstrate the versatility of a new instrumental setup, capable of recording decay emission kinetics with lifetimes from nanosecond to microseconds. Conclusions: While the combined wavelength approach for the imaging of emissions from different materials has been demonstrated for the study of ancient Egyptian pigments (both organic and inorganic), the method could be extended to the analysis of modern pigments and paintings

Effetti della ridotta dimensionalità e dell’ ordinamento sulle proprietà di ossidi dei metalli di transizione caratterizzati da elettroni fortemente correlati.

2011/2012Nel vasto scenario dei materiali fortemente correlati gli ossidi dei metalli di transizione hanno attratto enorme interesse a causa delle loro interessanti proprietà fisiche, come ad esempio, la superconduttività nei cuprati e la magnetoresistenza gigante nelle manganiti. In particolare, il mio interesse è stato rivolto ad una specifica classe di materiali, per i quali la dimensionalità è il parametro più importante. Le attività sperimentali sono state focalizzate verso due sistemi: la manganite Pr0.5Ca1.5MnO4 dopata a metà e a strato singolo (hd-PCMO) e la famiglia dei rutenati Srn+1RunO3n+1 (n=1,2,3). Entrambi questi sistemi esibiscono fenomeni affascinanti strettamente legati ad una complicata interazione tra i gradi di libertà del reticolo cristallino, di spin, di carica, ed orbitale, dove la dimensionalità cristallina gioca un ruolo cruciale. Con il mio progetto di dottorato ho studiato alcune proprietà dei materiali sopracitati per mezzo di spettroscopie con raggi X, come l’emissione risonante di raggi X (RXES) e l’assorbimento di raggi X (XAS) statico e risolto in tempo. Tutte le misure sono state condotte utilizzando la linea di luce BACH (linea di luce per dicroismo avanzato) dell’anello di accumulazione Elettra della Elettra-Sincrotrone Trieste. Il sistema hd-PCMO presenta una transizione di ordinamento di carica ed orbitale (CO-O) ad una temperatura TCO relativamente elevate, i.e. 340 K, accompagnata da una distorsione strutturale ortorombica, dove i portatori di carica fortemente correlati eg del Mn si ordinano in sotto-reticoli cristallografici separati (stato di carica ordinato) con un carattere orbitale specifico (stato di ordinamento orbitale). Inoltre, hd-PCMO presenta anche una risposta reticolare anomala ad una temperatura 20 K sopra la temperatura di Neél TN, che è associata ad un inatteso accoppiamento spin-reticolo. Poiché mancava uno studio degli stati elettronici non occupati del PCMO, misure dipendenti dalla temperatura per mezzo del dicroismo lineare (XLD) sono state realizzate alle soglie K dell’ossigeno e L3 del Mn al fine di spiegare il ruolo della topologia orbitale dei Mn 3d – O 2p. I dati sperimentali, supportati da calcoli ab-initio LDA+U, ci danno informazioni sulla ridistribuzione di carica e sui cambiamenti delle p-DOS alla transizione CO-O e a quella antiferromagnetica (AFM). I risultati ottenuti mostrano che l’interazione competitiva tra la distorsione locale atomica, necessaria per permettere l’ordinamento CO, e le dinamiche di carica del meccanismo di hopping regolano lo stato orbitale dei portatori di carica. Inoltre, sulla base di studi teorici che predicono la formazione di fasi orbitali e strutturali transienti “nascoste” per mezzo della stimolazione ottica, abbiamo studiato le DOS non occupate dello stato metastabile indotto otticamente nel PCMO per mezzo della XAS risolta in tempo, che offre uno strumento unico per misurare le DOS proiettate in sito ed in simmetria degli stati metastabili della materia. Le misure XAS risolte in tempo alla soglia K dell’ossigeno sono state realizzate per mezzo di un nuovo apparato sperimentale disponibile a BACH, che si basa su un laser Ti:zaffiro (impulsi di pompa) con tasso di ripetizione variabile sincronizzato con gli impulsi a 500 MHz dei raggi X (impulsi di sonda). L’evoluzione temporale degli spettri XAS attraverso la transizione CO-O fotoindotta otticamente risulta differente rispetto alle misure XAS adiabatiche, dimostrando l’esistenza di una “fase nascosta” fotoindotta nel PCMO, la cui natura è ancora sconosciuta. I rutenati Srn+1RunO3n+1 (n=1,2,3) sono emersi come una famiglia importante di peroschiti a causa dell’evoluzione inattesa e senza precedenti dal comportamento anisotropico ferro- o metamagnetico del Sr4Ru3O10 (n=3) dipendente dalla direzione del campo magnetico, all’ aumentato paramagnetismo di Pauli vicino all’ordinamento magnetico del Sr3Ru2O7 (n=2) e, infine, alla superconduttività a bassa temperature in Sr2RuO4 (n=1). Nonostante vengano riportati numerosi studi sulle proprietà strutturali e magnetiche di questi composti, l’evoluzione delle strutture elettroniche occupate e non occupate non è stata investigata in dettaglio. Quindi, la dipendenza delle strutture elettroniche e l’ibridizzazione degli stati 2p dell’ossigeno sono state investigate combinando la spettroscopia XAS alla soglia K dell’ossigeno (transizione 2p-1s) dipendente dalla polarizzazione e la spettroscopia RXES. Una sezione del capitolo 3 è dedicata ad illustrare un setup sperimentale sviluppato recentemente per esperimenti XAS risolti in tempo sfruttando la struttura temporale “multibunch” dell’anello di accumulazione del sincrotrone. Sfruttando le potenzialità di questo setup, la transizione di superficie semiconduttore-metallo nel germanio cristallino è stata fotoindotta ed il set completo di dati viene discusso. Lo schema della mia tesi di dottorato è il seguente. Il primo capitolo presenta una panoramica dell’intero lavoro. Il secondo capitolo è diviso in due sezioni. La prima sezione introduce il lettore alla fisica orbitale ed alle transizioni di fase elettroniche nei metalli di transizione a ridotta dimensionalità, con un excursus sullo stato dell’arte dei composti 3d del manganese e la famiglia 4d dei rutenati. L’intento della seconda sezione è quello di spiegare l’importanza delle tecniche spettroscopiche nei raggi X molli come strumenti per investigare le proprietà elettroniche dei solidi. La descrizione delle spettroscopie XAS e RXES vengono riviste più in dettaglio nel capitolo 3, che include anche la descrizione dell’apparato sperimentale della beamline BACH e del laboratorio T-ReX al Sincrotrone Elettra. Il capitolo 4 è dedicato alla teoria funzionale di densità (DFT) ed alla approssimazione locale di densità più U (LDA+U) ed ai dettagli del modello del sistema hd-PCMO. Il capitolo 5, che presenta i casi studiati, è diviso in due sezioni: il caso del PCMO, che include le misure XAS statiche e risolte in tempo, ed il caso della serie Ruddlesden-Popper dei rutenati di Sr investigate per mezzo della RXES. Nel capitolo finale vengono presentati i commenti finali su questo lavoro.In the vast scenario of strongly correlated-electron materials transition-metal oxides have attracted enormous interest because of their interesting physical properties, including for example, superconductivity in cuprates and colossal magnetoresistance in manganites. In particular, my interest was directed to a particular class of materials, whose dimensionality is the most defining material parameter. With my Ph.D. project I deepened into some physical properties of these materials by means of core-levels spectroscopies such as resonant x ray emission (RXES) and static and time-resolved x ray absorption (XAS). All the measurements have been carried out at the beamline BACH (Beamline for Advanced diCHroism) at the Elettra light source facility in Trieste. The experimental activities focused on two case-study systems: the single layered half-doped Pr0.5Ca1.5MnO4 (hd-PCMO) and the layered Srn+1RunO3n+1 (n=1,2,3) family. Both these systems exhibit fascinating phenomena intimately related to a complicated interplay between the crystal lattice, spin, charge, and orbital degrees of freedom, where crystal dimensionality plays a crucial role. hd-PCMO exhibits a charge-orbital ordering (CO-O) transition at a remarkably high TCO, slightly above room temperature, accompanied by an orthorhombic structural distortion, where the strongly correlated Mn eg charge carriers order onto separate crystallographic sub-lattices (charge-ordered state) with a specific orbital character (orbital ordered state). Furthermore, hd-PCMO also displays an anomalous lattice response at temperatures 20K above the Neél temperature TN, which is associated to an unexpected spin-lattice coupling. Since a study of the PCMO unoccupied electronic states was lacking, temperature dependence measurements by XAS linear dichroism (XLD) have been performed at the O-K and Mn-L3 thresholds in order to elucidate the role of Mn 3d - O 2p orbital topology. The experimental data, supported by ab-initio LDA+U, shed light on the charge redistribution and p-DOS changes at the CO-O and antiferromagnetic (AFM) transitions. The results obtained show that the competitive interplay between the local atomic distortion, necessary for accomodating the CO-ordering, and the charge dynamics of the hopping mechanism regulates the orbital state of the charge carriers. Furthermore, on the basis of theoretical studies that predict the formation of transient “hidden” orbital and structural phases by optical stimulation, we have studied the unoccupied DOS of the optically induced metastable state in PCMO by means of time resolved XAS, which offers a unique tool to measure site and symmetry projected DOS of metastable states in matter. Tr-XAS measurements at the O-K edge have been carried out by means of a novel experimental apparatus available at BACH, which is based on a variable repetition rate Ti:sapphire laser (pump pulse) synchronized with the ∼ 500 MHz X-ray photon pulses (probe pulses). The time evolution of the XAS lineshapes across the optically photoinduced CO-O transition results different respect to the adiabatic XAS measurements, demonstrating the existence of a photoinduced “hidden phase” in PCMO, whose nature is still unknown. The layered Srn+1RunO3n+1 (n=1,2,3) have emerged as an important family of perovskites because of the unexpected and unprecedented evolution from anisotropic ferro- or metamagnetic behavior of Sr4Ru3O10 (n=3) dependent on the direction of the magnetic field, enhanced Pauli paramagnetism close to magnetic order of Sr3Ru2O7 (n=2) and, finally, to low-temperature superconductivity in Sr2RuO4 (n=1). Although numerous studies have been reported on the structural and magnetic properties of these compounds, the evolution of the occupied and unoccupied electronic structures were not investigated in detail. Thus, the dependence of electronic structures and the hybridization of O 2p states have been investigated by combining polarization dependent O K (2p-1s transition) XAS and RXES spectroscopies. A section of the chapter 3 is dedicated to illustrate a newly developed experimental setup for time-resolved XAS experiments by exploiting the multibunch time structure of a synchrotron storage ring. By exploiting the capabilities of this setup, the surface semiconductor-metal transition in crystalline germanium has been photoinduced and the complete set of data discussed. The outline of my Ph.D. thesis is the following. The first chapter presents an overview of the entire work. The second chapter is divided into two sections. The first section introduces the reader into the orbital physics and the electronic phase transitions in low dimensional transition metal oxides, with an excursus on the state of the art of 3d manganese compounds and the family of 4d Ruthenates. The second section is aimed to explain the importance of soft x-ray spectroscopic techniques as tools to investigate the electronic properties of solids. The description of XAS and RXES are reviewed in more details in chapter 3, which includes also the description of the experimental apparatus of BACH beamline and T-ReX lab at the Elettra synchrotron light source. Chapter 4 is dedicated to the Density Functional Theory (DFT) and Local Density Approximation plus U (LDA+U) theories and to the details of the modelling of the hd-PCMO system. Chapter 5, which presents the cases studied, is divided into two sections: the case of PCMO, including static and time resolved XAS measurements, and the case of Ruddlesden-Popper series of Sr Ruthenates investigated by means of RXES. In the final chapter the concluding remarks on this work are presented.XXV Ciclo198

Multianalytical Study of Historical Luminescent Lithopone for the Detection of Impurities and Trace Metal Ions

We have explored the performance of an integrated multianalytical approach to the analysis of a series of microsamples of historical lithopone (a coprecipitate of ZnS + BaSO₄) produced at the beginning of the 20th century, based on the combination of spectrally- and lifetime-resolved photoluminescence (PL) microscopy imaging and electron paramagnetic resonance (EPR) spectroscopy. Multispectral imaging of the PL emission from microsamples revealed the presence of different luminescence centers emitting in the visible spectrum, which we have hypothesized as trace Cu and Mn impurities unintentionally introduced into the ZnS crystal lattice during synthesis, which act as deep traps for electrons. Time-resolved PL imaging analyses highlighted the microsecond decay-kinetic behavior of the emission, confirming the trap state nature of the luminescence centers. EPR confirmed the presence of Cu and Mn, further providing information on the microenvironment of defects in the ZnS crystalline lattice related to specific paramagnetic ions. The multianalytical approach provides important insights into the historical synthesis of lithophone and will be useful for the rapid screening and mapping of impurities in complex semiconductor pigments and other artists’ materials

Photoluminescence properties of zinc white: an insight into its emission mechanisms through the study of historical artist materials

While the photophysical properties of ZnO nanostructures have been widely explored, less research has focused on the bulk material present in artist pigments. This study is based on the analysis of historical pastels, representative of artist materials available at the turn of the twentieth century, and of the pure powder pigment as the control sample. The study of the intensity of the photoluminescence emission as a function of the fluence and of the nanosecond and microsecond emission decay kinetic properties allows the elucidation of the emission mechanisms in control ZnO and historical samples containing ZnO. Data suggest that in historical samples the near-band-edge free-exciton photoluminescence emission, typically occurring in the pure semiconductor, is influenced by the interaction of the pigment with surrounding organic binding material. Conversely, crystal defects, typically expected in historical samples following the imperfect synthesis process available at the beginning of the twentieth century, introduce minor modifications to the photoluminescence emission. The study further suggests that zinc carboxylates, detected in all historical samples and known to introduce characteristic groups on the surface of ZnO, could be responsible for changes in emission mechanisms. Research demonstrates how photoluminescence decay kinetics and the study of the dependence of the emission intensity on the fluence are powerful methods for elucidating the nature of the mechanism processes in luminescent semiconductor pigments

Identification of pigments in different layers of illuminated manuscripts by X-ray fluorescence mapping and Raman spectroscopy

We propose a non-invasive approach for the study of illuminated manuscripts based on the combination of near-infrared reflectance imaging, X-ray fluorescence mapping, and Raman spectroscopy. Taking advantage of the different absorption coefficient of the characteristic X-ray emission lines of a specific element, we have implemented a differential mapping method to distinguish the X-ray emissions from two paint layers of a manuscript. This approach was applied to a coat-of-arms of a precious illuminated manuscript belonging to the Trivulziana library collection and revealed specific patterns through the mapping of the spatial distribution of lead in different paint layers. Multivariate methods, including principal component analysis and non-negative matrix factorization, applied to the X-ray fluorescence mapping dataset demonstrate the spatial correlation between different elements. The use of complementary Raman and X-ray fluorescence spectroscopy has hence permitted the identification of the pigments employed in the original and overpainting layers found on the coat-of-arms. Through analysis, it was possible to identify the patron of the Salterium, attributed to Fracesco dei librai, as 15th C. bishop Bernardo de' Rossi

An integrated approach based on micro-mapping analytical techniques for the detection of impurities in historical Zn-based white pigments

In this work we propose an integrated approach, based on synchrotron analysis with micrometric spatial resolution and sub-ppm sensitivity and m-Raman mapping, for investigating impurities and heterogeneous inclusions in historical samples of Zn-based white pigments. Analysis was performed at the LUCIA beamline at the SOLEIL synchrotron radiation facility for the simultaneous detection of the elemental distribution in suitably prepared pigment samples using micro-X-ray fluorescence (m-XRF) mapping and for the investigation of oxidation states and coordination of metals using micro-X-ray near edge absorption (m-XANES) spectroscopy. The identification of specific molecular signatures and the detection of their spatial distribution throughout samples by m-Raman measurements supported and complemented X-ray analysis, allowing the identification of Cr- and Fe-based inclusions in historical samples. In ZnO pigments, common impurities are due to the production process and include Fe and, depending on samples, Cd, Cl and Pb. In one of the Zn-containing pigments, identified as Lithopone, m-XRF mapping revealed the presence of Co, both as highly concentrated micrometric inclusions and as impurities throughout the pigment

Multi-analytical non-invasive study of modern yellow paints from postwar Italian paintings from the International Gallery of Modern Art Cà Pesaro, Venice

We present a multi-analytical non-invasive approach for the characterization of yellow paints used in three paintings from the International Gallery of Modern Art Cà Pesaro, Venice. The paintings selected for this study were executed in oil-based media between 1940-1960, they are unvarnished and have large monochromatic yellow areas. We focus on the identification of yellow pigments with a combined approach based on non-invasive portable X-ray Fluorescence (XRF) spectrometry, complemented with VIS reflectance, remote-Fourier Transform Infrared and Raman spectroscopies. Different yellow pigments including Chrome yellow Naples Yellow and Cadmium-based yellow were identified. Their identification is of fundamental importance since several modern inorganic yellow pigments (in particular chrome and cadmium-based pigments) are known to exhibit peculiar degradation patterns, leading to noteworthy aesthetic changes in paint such as darkening and fading.This work highlights the suitability of non-destructive techniques for the characterisation of modern paints and the utility of an integrated approach to obtain useful information for preventive conservation. Results demonstrate the need to complement elemental data acquired using portable XRF with suitable complementary molecular spectroscopic techniques