Search

Ramon & Cajal research contract (RYC-2015-18932) from the Spanish Ministry of Economy, Industry and Competitiveness

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure-temperature-time (P-T-t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P-T-t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P-T-t trajectory. The results of garnet growth simulation can be used to infer the P-T-t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion

Magnesian metamorphic rocks with metapelitic mineral assemblage and composition are of great interest in metamorphic petrology for their ability to constrain P-T conditions in terranes where metamorphism is not easily visible. Phase-assemblage diagrams for natural and model magnesian metapelites in the system KFMASH are presented to document how phase relationships respond to water activity, bulk composition, pressure and temperature. The phase assemblages displayed on these phase diagrams are consistent with natural mineral assemblages occurring in magnesian metapelites. It is shown that the equilibrium assemblages at high pressure conditions are very sensitive to a(H2O). Specifically, the appearance of the characteristic HP assemblage chloritoid-talc-phengite-quartz (with excess H2O) in the magnesian metapelites of the Monte Rosa nappe (Western Alps) is due to the reduction of a(H2O). Furthermore, the mineral assemblages are determined by the whole-rock FeO/(FeO+MgO) ratio and effective Al content X A as well as P and T. The predicted mineral associations for the low- and high-X A model bulk compositions of magnesian metapelites at high pressure are not dependent on the X A variations as they show a similar sequence of mineral assemblages. Above 20kbar, the prograde sequence of assemblages associated with phengite (with excess SiO2 and H2O) for low- and high-X A bulk compositions of magnesian metapelites is: carpholite-chlorite→chlorite-chloritoid→chloritoid-talc→chloritoid-talc-kyanite→ talc-garnet-kyanite→garnet-kyanite±biotite. At low to medium P-T conditions, a low-X A stabilises the phengite-bearing assemblages associated with chlorite, chlorite+K-feldspar and chlorite+biotite while a high-X A results in the chlorite-phengite bearing assemblages associated with pyrophyllite, andalusite, kyanite and carpholite. A high-X A magnesian metapelite with nearly iron-free content stabilises the talc-kyanite-phengite assemblage at moderate to high P-T conditions. Taking into account the effective bulk composition and a(H2O) involved in the metamorphic history, the phase-assemblage diagrams presented here may be applied to all magnesian metapelites that have compositions within the system KFMASH and therefore may contribute to gaining insights into the metamorphic evolution of terranes. As an example, the magnesian metapelites of the Monte Rosa nappe have been investigated, and an exhumation path with P-T conditions for the western roof of the Monte Rosa nappe has been derived for the first time. The exhumation shows first a near-isothermal decompression from the Alpine eclogite peak conditions around 24kbar and 505°C down to approximately 8kbar and 475°C followed by a second decompression with concomitant cooling

Garnet in metapelites from the Wölz Complex of the Austroalpine crystalline basement east of the Tauern Window characteristically consists of two growth phases, which preserve a comprehensive record of the geothermal history during polymetamorphism. From numerical modelling of garnet formation, detailed information on the pressure-temperature-time (P-T-t) evolution during prograde metamorphism is obtained. In that respect, the combined influences of chemical fractionation associated with garnet growth, modification of the original growth zoning through intragranular diffusion and the nucleation history on the chemical zoning of garnet as P and T change during growth are considered. The concentric chemical zoning observed in garnet and the homogenous rock matrix, which is devoid of chemical segregation, render the simulation of garnet growth through successive equilibrium states reliable. Whereas the first growth phase of garnet was formed at isobaric conditions of ∼3.8kbar at low heating/cooling rates, the second growth phase grew along a Barrovian P-T path marked with a thermal peak of ∼625°C at ∼10kbar and a maximum in P of ∼10.4kbar at ∼610°C. For the heating rate during the growth of the second phase of garnet, average rates faster than 50°CMa−1 are obtained. From geochronological investigations the first growth phase of garnet from the Wölz Complex pertains to the Permian metamorphic event. The second growth phase grew in the course of Eo-Alpine metamorphism during the Cretaceous

East African landscapes today are the result of the cumulative effects of climate and land-use change over millennial timescales. In this review, we compile archaeological and palaeoenvironmental data from East Africa to document land-cover change, and environmental, subsistence and land-use transitions, over the past 6000 years. Throughout East Africa there have been a series of relatively rapid and high-magnitude environmental shifts characterised by changing hydrological budgets during the mid- to late Holocene. For example, pronounced environmental shifts that manifested as a marked change in the rainfall amount or seasonality and subsequent hydrological budget throughout East Africa occurred around 4000, 800 and 300 radiocarbon years before present (yr BP). The past 6000 years have also seen numerous shifts in human interactions with East African ecologies. From the mid-Holocene, land use has both diversified and increased exponentially, this has been associated with the arrival of new subsistence systems, crops, migrants and technologies, all giving rise to a sequence of significant phases of land-cover change. The first large-scale human influences began to occur around 4000 yr BP, associated with the introduction of domesticated livestock and the expansion of pastoral communities. The first widespread and intensive forest clearances were associated with the arrival of iron-using early farming communities around 2500 yr BP, particularly in productive and easily-cleared mid-altitudinal areas. Extensive and pervasive land-cover change has been associated with population growth, immigration and movement of people. The expansion of trading routes between the interior and the coast, starting around 1300 years ago and intensifying in the eighteenth and nineteenth centuries CE, was one such process. These caravan routes possibly acted as conduits for spreading New World crops such as maize (Zea mays), tobacco (Nicotiana spp.) and tomatoes (Solanum lycopersicum), although the processes and timings of their introductions remains poorly documented. The introduction of southeast Asian domesticates, especially banana (Musa spp.), rice (Oryza spp.), taro (Colocasia esculenta), and chicken (Gallus gallus), via transoceanic biological transfers around and across the Indian Ocean, from at least around 1300 yr BP, and potentially significantly earlier, also had profound social and ecological consequences across parts of the region.

A thermodynamic model for the quaternary white mica solid solution with end-members muscovite-Mg-celadonite-paragonite-Fe-celadonite (Ms-MgCel-Pg-FeCel) is presented. The interaction energies for the MgCel-Pg join, the FeCel-Pg join and the ternary interactions were obtained from natural coexisting phengite-paragonite pairs. Phengite-paragonite pairs were selected based on the criteria that their chemical compositions may be represented as a linear combination of the model end-member compositions and that the respective formation conditions (350-650°C, 4-21 kbar) are accurately known. Previously published excess free energy expressions were used for the Ms-Pg, Ms-MgCel and Ms-FeCel binaries. The suggested mixing model was tested by calculating multicomponent equilibrium phase diagrams. This proved to be particularly well suited to reproduce compositional variations of white micas from amphibolite-facies metapelites

The metamorphic evolution of metapelites from the eastern part of the Monte Rosa nappe and the Camughera-Moncucco unit, both situated in the upper Penninic units SW of the Simplon line, were investigated using microstructural relationships and equilibrium phase diagrams. The units under consideration experienced pre-Alpine amphibolite-facies conditions and underwent a complex metamorphic evolution during the Alpine orogeny. Peak pressures during an early Alpine high-pressure stage of 12·5-16 kbar were similar in the Monte Rosa nappe and Camughera-Moncucco unit. A pronounced thermal gradient is indicated during decompression leading to an amphibolite-facies overprint, as the decompression paths went through the chlorite, biotite and plagioclase stability fields in most of the Monte Rosa nappe, through the staurolite field in the easternmost Monte Rosa nappe and in the Camughera-Moncucco unit, and through the sillimanite field in the easternmost Camughera-Moncucco unit. In high-Al metapelites the initial formation of staurolite is related to continuous paragonite breakdown and associated formation of biotite. In the course of this reaction phengite becomes successively sodium enriched. In low-Al metapelites, in contrast, the initial staurolite formation occurs via the continuous breakdown of sodium-rich phengite. In both low- and high-Al metapelites the largest volume of staurolite is formed during the continuous breakdown of sodium-rich phengite below P-T conditions of about 9·5 kbar at 600-650°C. During this reaction phengite becomes successively potassium enriched as sodium from phengite is used to form the albite component in plagioclase. For ‘normal' pelitic chemistries, phengite becomes Na enriched during decompression through the breakdown of paragonite along a near-isothermal decompression path. The Na content in phengite reaches its maximum when paragonite is entirely consumed. During further decompression the paragonite component in phengite decreases again because Na is preferentially incorporated into the albite component of plagioclase

I concentratori solari luminescenti (LSCs) sono delle guide d’onda composti da una matrice polimerica drogata o ricoperta con fluorofori. La luce solare diretta e/o diffusa che penetra nella matrice è assorbita dai fluorofori e poi riemessa dagli stessi con energia minore. La luce emessa, grazie alla riflessione totale interna, propaga fino a raggiungere i bordi della guida d’onda dove è convertita in elettricità da celle fotovoltaiche poste sul perimetro della matrice. L’efficienza del dispositivo è ridotta da numerosi processi di perdita, sia dovuti alla riflessione della matrice e al cono di fuga, sia quelli che dipendono dalle caratteristiche dei fluorofori, come il coefficiente di assorbimento, il quantum yield (QY) di fotoluminescenza (PL) e il riassorbimento. Per minimizzare tali perdite, una buona alternativa ai tradizionali fluorofori sono i quantum dots (QDs) colloidali che presentano solitamente un elevato QY, un alto coefficiente di assorbimento e una lunghezza d’onda di emissione controllabile cambiando le dimensioni dei nanocristalli tramite modifiche dei parametri di sintesi. Inoltre, ingegnerizzando opportunamente i QDs, è possibile realizzare particelle con elevato Stokes-shift tra gli spettri di assorbimento ed emissione, in modo da ridurre quanto più possibile il riassorbimento. Il progetto si è quindi focalizzato sullo sviluppo della sintesi di QDs, al fine di ottimizzare il QY di fotoluminescenza, la compatibilizzazione con la matrice polimerica e la fotostabilità, limitando comunque il riassorbimento. Inoltre. la procedura di sintesi deve essere facilmente trasportabile su volumi industriali, per soddisfare il fabbisogno di produzioni di elevati metri quadrati di LSCs. Durante i tre anni di progetto di dottorato in Alto Apprendistato ho potuto sviluppare una procedura di sintesi che consiste in quattro step: • crescita di nanocristalli di CuInS2 core; • formazione del quaternario tramite aggiunta di zinco (ZnCuInS2); passaggio cruciale per aumentare il QY e controllare la lunghezza d’onda di emissione; • crescita di una shell di solfuro di zinco (ZnCuINS2/ZnS) per passivare la superficie dei nanocristalli, aumentare il QY e la fotostabilità; • trattamento post sintesi di scambio di leganti parziale per migliorare la solubilità nella matrice polimerica. I nanocristalli così prodotti mostrano un QY del 60% ed un’ottima solubilità nella matrice polimerica. Infatti, è stato prodotto un LSC di grande dimensione (30 cm x 30 cm x 0.7 cm) la cui optical power efficiency, OPE = 6.8%. Inizialmente ho sviluppato la procedura di sintesi in un pallone di vetro da 25 mL, producendo 250 mg a sintesi. Grazie all’attrezzatura fornita da Glass to Power S.p.A ho potuto studiare lo scale-up della sintesi. Dapprima ho effettuato studi preliminare, per approfondire alcune possibili problematiche dovute all’aumento dei volumi, su palloni di maggiori dimensioni, 500 mL e 2 L. Analizzate e risolte le tematiche di riscaldamento e stop della sintesi ho effettuato sintesi in un reattore preindustriale producendo 300 g di nanocristalli di ZnCuINS2/ZnS. Oltre ad incrementare la produzione di sintesi da 250 mg a 300 g mi sono occupata dell’ottimizzazione della procedura di sintesi. Ho testato diverse strategie per incrementare il QY senza danneggiare la solubilità nel polimero. Grazie ad una variazione di reagente nel secondo step e ad un incremento dei layer della shell ho ottenuto nanocristalli con 80% di QY. Il prossimo step sarà effettuare lo scale-up di questa nuova procedura e produrre LSC di grandi dimensioni. Grazie alle collaborazioni con altri studenti di dottorato ho sintetizzato nanocristalli di calcogenuro drogati oro e opportunamente decorati con molecole coniugate per sistemi di up-conversion. Grazie all’introduzione dell’oro in questi sistemi si è ottenuta un’efficienza di up-conversion del 12%. Luminescent solar concentrators (LSCs) are waveguides composed of a polymeric matrix doped or coated with fluorophores. The direct and/or diffuse sunlight that penetrates the matrix is absorbed by the fluorophores and then re-emitted by them with less energy. The light emitted, thanks to the total internal reflection, propagates until it reaches the edges of the wave guide where it is converted into electricity by photovoltaic cells placed on the perimeter of the matrix. The efficiency of the device is reduced by numerous loss processes, due to the reflection of the matrix and the escape cone, and/or due to the characteristics of the fluorophores, such as the absorption coefficient, the quantum yield (QY) of photoluminescence (PL) and the reabsorption. To minimize losses due to fluorophores, a good alternative are colloidal quantum dots (QDs) that usually have a high QY, a high absorption coefficient and a controllable emission wavelength by changing the size of the nanocrystals. Furthermore, by properly engineering the QDs, it is possible to realize particles with high Stokes-shift between the absorption and emission spectra, in order to reduce the reabsorption as much as possible. The project is focused on the development of the synthesis of QDs, in order to optimize the QY of photoluminescence, compatibility with the polymer matrix and photostability, while limiting the reabsorption. Besides. the synthesis procedure must be easily transferable on industrial volumes, to meet the production needs of high square meters of LSCs. During the three years of the doctoral project in High Apprenticeship I was able to develop a synthesis procedure consisting of four steps: • growth of CuInS2 core nanocrystals; • quaternary formation with zinc addition (ZnCuInS2); crucial step to increase the QY and control the emission wavelength; • growth of a zinc sulphide shell (ZnCuInS2/ZnS) to passivate the surface of nanocrystals, increase QY and photostability; • post-synthesis treatment of the partial exchange of ligands to improve solubility in the polymer matrix. The nanocrystals thus produced show 60% QY and excellent solubility in the polymer matrix. In fact, a large size LSC (30 cm x 30 cm x 0.7 cm) was produced, whose optical power efficiency, OPE = 6.8%. Initially, I developed the synthesis procedure in a 25 ml glass flask, producing 250 mg for batch. Thanks to the equipment provided by Glass to Power s.p.A I was able to study the increase in the scale of the synthesis. Firstly, in order to investigate some possible problems due to the increase in volumes, I have carried out preliminary studies on larger balloons, 500 mL and 2 L. After analysis of heating and quenching of synthesis, I have performed the synthesis in a preindustrial reactor producing 300 g of nanocrystals of ZnCuInS2/ZnS. In addition I also optimized the synthesis procedure. I tested several strategies to increase QY without damaging solubility in the polymer. Thanks to a variation of the reagent in the second step and an increase of the shell layers, I obtained nanocrystals with 80% of QY. The next step will be to scale up this new procedure and produce large LSCs. I collaborated with other PhD students, in particular, I synthesized with a heat-up method CdSe nanocrystals doped with Au7 clusters and decorated with conjugated dyes as efficient triplet sensitizers or up-conversion applications (gold doping improves up-conversion efficiency). The beneficial effects of the doping strategy result in a maximum UC efficiency of 12%, which is an unprecedented result for up-conversion based on decorated NCs as triplet sensitizers.

Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.

Low-power photon upconversion (UC) based on sensitized triplet-triplet annihilation (sTTA) is considered as the most promising upward wavelength-shifting technique to enhance the light-harvesting capability of solar devices. Colloidal nanocrystals (NCs) with conjugated organic ligands have been recently proposed to extend the limited light-harvesting capability of molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitize free annihilator moieties responsible for the upconverted luminescence. The ET efficiency is typically limited by parasitic processes, above all nonradiative hole-transfer to the ligand highest occupied molecular orbital (HOMO). Here, a new exciton-manipulation approach is demonstrated that enables loss-free ET by electronically doping CdSe NCs with gold impurities that introduce a hole-accepting intragap state above the HOMO energy of 9-anthracene acid ligands. Upon photoexcitation, the NC photoholes are rapidly routed to the Au-level, producing a long-lived bound exciton in perfect resonance with the ligand triplet. This hinders hole-transfer leading to ≈100% efficient ET that translates into an upconversion quantum yield as high as ≈12% (≈24% in the normalized definition), which is the highest performance for NC-based upconverters based on sTTA to date and approaches the record efficiency of optimized organic systems.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

Metal clusters with appropriate molecular ligands have been shown to be suitable subnanometer building blocks for supramolecular architectures with controlled secondary interactions, providing access to physical regimes not achievable with conventional intermolecular motifs. An example is the excimer photophysics exhibited by individual cluster-based superstructures produced by top-down etching of gold nanoparticles. Now, a supramolecular architecture of copper clusters is presented with controlled optical properties and efficient non-resonant luminescence produced via a novel bottom-up synthesis using mild green reductants followed by a ligand exchange reaction and spontaneous supramolecular assembly. Spectroscopic experiments confirm the formation of the intercluster network and reveal the permanent nature of their excimer-like behavior, thus extending the potential impact and applicability of metal cluster superstructures as efficient and stable non-resonant single-particle emitters.

Ternary I-III-VI2 nanocrystals (NCs), such as CuInS2, are receiving attention as heavy-metals-free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio-imaging. The origin of the optical properties of CuInS2 NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes-shifted and long-lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect-free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low-bandgap NCs would be accompanied by increased re-absorption losses. Here, by studying stoichiometric CuInS2 NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band-edge exciton, thus supporting the VB-structure model. At very low temperatures, the NCs also show dark-state emission likely originating from enhanced electron-hole spin interaction. The impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray-tracing simulations. Based on the emerging device design guidelines, optical-grade large-area (30x30 cm(2)) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large-area devices.