Porous silicon technology for integrated microsystems

With the development of micro systems, there is an increasing demand for integrable porous materials. In addition to those conventional applications, such as filtration, wicking, and insulating, many new micro devices, including micro reactors, sensors, actuators, and optical components, can benefit from porous materials. Conventional porous materials, such as ceramics and polymers, however, cannot meet the challenges posed by micro systems, due to their incompatibility with standard micro-fabrication processes. In an effort to produce porous materials that can be used in micro systems, porous silicon (PS) generated by anodization of single crystalline silicon has been investigated. In this work, the PS formation process has been extensively studied and characterized as a function of substrate type, crystal orientation, doping concentration, current density and surfactant concentration and type. Anodization conditions have been optimized for producing very thick porous silicon layers with uniform pore size, and for obtaining ideal pore morphologies. Three different types of porous silicon materials: meso porous silicon, macro porous silicon with straight pores, and macro porous silicon with tortuous pores, have been successfully produced. Regular pore arrays with controllable pore size in the range of 2µm to 6µm have been demonstrated as well. Localized PS formation has been achieved by using oxide/nitride/polysilicon stack as masking materials, which can withstand anodization in hydrofluoric acid up to twenty hours. A special etching cell with electrolytic liquid backside contact along with two process flows has been developed to enable the fabrication of thick macro porous silicon membranes with though wafer pores. For device assembly, Si-Au and In-Au bonding technologies have been developed. Very low bonding temperature (~200 degrees C) and thick/soft bonding layers (~6µm) have been achieved by In-Au bondi ng technology, which is able to compensate the potentially rough surface on the porous silicon sample without introducing significant thermal stress. The application of the porous silicon material in micro systems has been demonstrated in a micro gas chromatograph system by two indispensable components: an integrated vapor source and an inlet filter, wherein porous silicon performs the basic functions of porous media: wicking and filtration. By utilizing a macro porous silicon wick, the calibration vapor source was able to produce a uniform and repeatable vapor generation for n-decane with less than a 0.1% variation in 9 hours, and less than a 0.5% variation in rate over 7 days. With engineered porous silicon membranes the inlet filter was able to show a depth filtration with nearly 100% collection efficiency for particles larger than 0.3µm in diameter, a low pressure-drop of 523Pa at 20sccm flow rate, and a filter capacity of 500µg/cm2.

Amplified bioproductivity during Transition IV (332 000-342 000 yr ago): evidence from the geochemical record of Lake El'gygytgyn

Abstract. To date, terrestrial archives of long-term climatic change within the Arctic have widely been restricted to ice cores from Greenland and, more recently, sediments from Lake El’gygytgyn in northeast Arctic Russia. Sediments from this lake contain a paleoclimate record of glacialinterglacial cycles during the last three million years. Lowresolution studies at this lake have suggested that changes observed during Transition IV (the transition from marine isotope stage (MIS) 10 to MIS 9) are of greater amplitude than any observed since. In this study, geochemical parameters are used to infer past climatic conditions thus providing the first high-resolution analyses of Transition IV from a terrestrial Arctic setting. These results demonstrate that a significant shift in climate was subsequently followed by a rapid increase in biogenic silica (BSi) production. Following this sharp increase, bioproductivity remained high, but variable, for over a thousand years. This study reveals differences in the timing and magnitude of change within the ratio of silica to titanium (Si/Ti) and BSi records that would not be apparent in lower resolution studies. This has significant implications for the increasingly common use of Si/Ti data as an alternative to traditional BSi measurements.

The Crystal Chemistry of Holtite

Holtite, approximately (Al,Ta,square)Al(6)(BO(3))(Si,Sb(3+),As(3+))(Sigma 3)O(12)(O,OH,square)(Sigma 3), is a member of the dumortierite group that has been found in pegmatite, or alluvial deposits derived from pegmatite, at three localities: Greenbushes, Western Australia; Voron'i Tundry, Kola Peninsula, Russia; and Szklary, Lower Silesia, Poland. Holtite can contain >30 wt.% Sb(2)O(3), As(2)O(3), Ta(2)O(5), Nb(2)O(5), and TiO(2) (taken together), but none of these constituents is dominant at a crystallographic site, which raises the question whether this mineral is distinct from dumortierite. The crystal structures of four samples from the three localities have been refined to R(1) = 0.02-0.05. The results show dominantly: Al, Ta, and vacancies at the Al(1) position; Al and vacancies at the Al(2), (3) and (4) sites; Si and vacancies at the Si positions; and Sb, As and vacancies at the Sb sites for both Sb-poor (holtite I) and Sb-rich (holtite II) specimens. Although charge-balance calculations based on our single-crystal structure refinements suggest that essentially no water is present, Fourier transform infrared spectra confirm that some OH is present in the three samples that could be measured. By analogy with dumortierite, the largest peak at 3505-3490 cm(-1) is identified with OH at the O(2) and O(7) positions. The single-crystal X-ray refinements and FTIR results suggest the following general formula for holtite: Al(7-[5x+y+z]/3)(Ta,Nb)(x)square([2x+y+z]/3)BSi(3-y)(Sb,As)(y)O(18-y-z)(OH)(z), where x is the total number of pentavalent cations, y is the total amount of Sb + As, and z <= y is the total amount of OH. Comparison with the electron microprobe compositions suggests the following approximate general formulae Al(5.83)(Ta,Nb)(0.50)square(0.67)BSi(2.50)(Sb,As)(0.50)O(17.00)(OH)(0.50) and Al(5.92)(Ta,Nb)(0.25)square(0.83)BSi(2.00)(Sb,As)(1.00) O(16.00)(OH)(1.00) for holtite I and holtite II respectively. However, the crystal structure refinements do not indicate a fundamental difference in cation ordering that might serve as a criterion for recognizing the two holtites as distinct species, and anion compositions are also not sufficiently different. Moreover, available analyses suggest the possibility of a continuum in the Si/(Sb + As) ratio between holtite I and dumortierite, and at least a partial continuum between holtite I and holtite II. We recommend that use of the terms holtite I and holtite II be discontinued.

Dating polygenetic metamorphic assemblages along a transect across the Western Alps

Multichronometric analyses were performed on samples from a transect in the French-Italian Western Alps crossing nappes derived from the Briançonnais terrane and the Piemonte-Liguria Ocean, in an endeavour to constrain the high-pressure (HP) metamorphism and the retrogression history. 12 samples of white mica were analysed by 39Ar-40Ar stepwise heating, complemented by 2 samples from the Monte Rosa 100 km to the NE and also attributed to the Briançonnais terrane. One Sm-Nd and three Lu-Hf garnet ages from eclogites were also obtained. White mica ages decrease from ca. 300 Ma in the westernmost samples (Zone Houillère), reaching ca. 300 °C during Alpine metamorphism, to < 48 Ma in the internal units to the East, which reached ca. 500 °C during Alpine orogeny. The conventional “thermochronological” interpretation postulates Cretaceous Eo-Alpine HP metamorphism and younger “cooling ages” in the higher-temperature samples. However, Eocene Lu-Hf and Sm-Nd ages from the same samples cannot be interpreted as post-metamorphic cooling ages, which makes a Cretaceous eclogitization untenable. The age date from this transect require instead to replace conventional “thermochronology” by an approach combining age dating with detailed geochemical, petrological and microstructural investigations. Petrology reveals important mineralogical differences along the transect. Samples from the Zone Houillère mostly contain detrital mica. White mica with Si > 6.45 atoms per formula unit becomes more abundant eastward. Across the whole traverse, HP phengitic mica forms the D1 foliation. Syn-D2 mica is Si-poorer and associated with nappe stacking, exhumation, and hydrous retrogression under greenschist facies conditions. D1 phengite is very often corroded, overgrown or intergrown by syn-D2 muscovite. Most importantly, syn-D2 recrystallization is not limited to S2 schistosity domains; microchemical fingerprinting shows that it also can form pseudomorphs after crystals that could be mistaken to have formed during D1 based on microstructural arguments alone. Thereby the Cl concentration in white mica is a useful discriminator, since D2 retrogression was associated with a less saline fluid than eclogitization. Once the petrological stage is set, geochronology is straightforward. All samples contain mixtures of detrital, syn-D1 and syn-D2 mica, and retrogression phases (D3) in greatly varying proportions according to local pressure-temperature-fluid activity-deformation conditions. The correlation of age vs. Cl/K clearly identifies 47 ± 1 Ma as the age of formation of syn-D1 mica along the entire transect, including the Monte Rosa nappe samples. The inferred age of the greenschist-facies low-Si syn-D2 mica generation ranges within 39-43 Ma, with local variations. Coexistence of D1 and D2 ages, and the constancy of non-reset D1 ages along the entire transect, are strong evidence that the D1 white mica ages are very close to formation ages. Volume diffusion of Ar in white mica (activation energy E = 250 kJ/mol; pressure-adjusted diffusion coefficient D’0 < 0.03 cm2 s-1) has a subordinate effect on mineral ages compared to both prograde and retrograde recrystallization in most samples. Eocene Lu-Hf and Sm-Nd garnet ages are prograde and predate the HP peak.

Systemic inflammation is higher in peripheral artery disease than in stable coronary artery disease.

OBJECTIVE The knowledge on the level of systemic inflammation in peripheral artery disease (PAD) is less well established than that in coronary artery disease (CAD). Systemic inflammation frequently coincides with atherosclerosis, but also with various traits of the metabolic syndrome (MetS). The individual contribution of CAD, PAD, and the MetS to inflammation is not known. METHODS We enrolled a total of 1396 patients, 460 patients with PAD Fontaine stages IIa-IV verified by duplex ultrasound (PAD group) and 936 patients free of limb claudication undergoing coronary angiography, of whom 507 had significant CAD with coronary stenoses ≥50% (CAD group), and 429 did not have significant CAD at angiography (control group). RESULTS C-reactive protein (CRP) was significantly higher in the PAD than in the CAD or in the control group (0.86 ± 1.85 mg/dl versus 0.44 ± 0.87 mg/dl and 0.39 ± 0.52 mg/dl, respectively, p < 0.001 for both comparisons). These significant differences were confirmed when patients with and subjects without the MetS were analyzed separately. In particular, within the PAD group, CRP was significantly higher in patients with the MetS than in subjects without the MetS (1.04 ± 2.01 vs. 0.67 ± 1.64 mg/dl; p = 0.001) and both, the presence of PAD and the MetS proved to be independently associated with CRP in analysis of covariance (F = 31.84; p < 0.001 and F = 10.52; p = 0.001, respectively). CONCLUSION Inflammatory activity in PAD patients is higher than in CAD patients and is particularly high in PAD patients affected by the MetS. Low grade systemic inflammation is independently associated with both the MetS and PAD.

Beneficial Effects of a Semi-Intensive Stroke Unit are Beyond the Monitor.

BACKGROUND AND PURPOSE Precise mechanisms underlying the effectiveness of the stroke unit (SU) are not fully established. Studies that compare monitored stroke units (semi-intensive type, SI-SU) versus an intensive care unit (ICU)-based mobile stroke team (MST-ICU) are lacking. Although inequalities in access to stroke unit care are globally improving, acute stroke patients may be admitted to Intensive Care Units for monitoring and followed by a mobile stroke team in hospital's lacking an SU with continuous cardiovascular monitoring. We aimed at comparing the stroke outcome between SI-SU and MST-ICU and hypothesized that the benefits of SI-SU are driven by additional elements other than cardiovascular monitoring, which is equally offered in both care systems. METHODS In a single-center setting, we compared the unfavorable outcomes (dependency and mortality) at 3 months in consecutive patients with ischemic stroke or spontaneous intracerebral hemorrhage admitted to a stroke unit with semi-intensive monitoring (SI-SU) to a cohort of stroke patients hospitalized in an ICU and followed by a mobile stroke team (MST-ICU) during an equal observation period of 27 months. Secondary objectives included comparing mortality and the proportion of patients with excellent outcomes (modified Rankin Score (mRS) 0-1). Equal cardiovascular monitoring was offered in patients admitted in both SI-SU and MST-ICU. RESULTS 458 patients were treated in the SI-SU and compared to the MST-ICU (n = 370) cohort. The proportion of death and dependency after 3 months was significantly improved for patients in the SI-SU compared to MST-ICU (p < 0.001; aOR = 0.45; 95% CI: 0.31-0.65). The shift analysis of the mRS distribution showed significant shift to the lower mRS in the SI-SU group, p < 0.001. The proportion of mortality in patients after 3 months also differed between the MST-ICU and the SI-SU (p < 0.05), but after adjusting for confounders this association was not significant (aOR = 0.59; 95% CI: 0.31-1.13). The proportion of patients with excellent outcome was higher in the SI-SU (59.4 vs. 44.9%, p < 0.001) but the relationship was no more significant after adjustment (aOR = 1.17; 95% CI: 0.87-1.5). CONCLUSIONS Our study shows that moving from a stroke team in a monitored setting (ICU) to an organized stroke unit leads to a significant reduction in the 3 months unfavorable outcome in patients with an acute ischemic or hemorrhagic stroke. Cardiovascular monitoring is indispensable, but benefits of a semi-intensive Stroke Unit are driven by additional elements beyond intensive cardiovascular monitoring. This observation supports the ongoing development of Stroke Centers for efficient stroke care. © 2015 S. Karger AG, Basel.

A Maximum Radius for Habitable Planets

We compute the maximum radius a planet can have in order to fulfill two constraints that are likely necessary conditions for habitability: 1- surface temperature and pressure compatible with the existence of liquid water, and 2- no ice layer at the bottom of a putative global ocean, that would prevent the operation of the geologic carbon cycle to operate. We demonstrate that, above a given radius, these two constraints cannot be met: in the Super-Earth mass range (1-12 M-earth), the overall maximum that a planet can have varies between 1.8 and 2.3 R-earth. This radius is reduced when considering planets with higher Fe/Si ratios, and taking into account irradiation effects on the structure of the gas envelope.

Chemistry of hot waters sampled from basaltic basement at DSDP Hole 83-504B

Seawater that has been altered by reaction with basaltic basement has been sampled from Deep Sea Drilling Project Hole 504B, located on 5.9-m.y.-old crust on the southern flank of the Costa Rica Rift. Fourteen water samples have been collected on Legs 69, 70, and 83, both before and after renewed drilling on the latter two legs, at temperatures from 69 to 133°C and pressures from 390 to 425 bars. The water sampled prior to renewed drilling on Leg 83 had occupied the hole for nearly 2 yr. since it was last flushed with surface seawater at the end of Leg 70. Despite some contamination by seawater during sampling, the composition of two of these waters has been determined by using nitrate as a tag for the contaminant. Both the 80 and 115°C waters have seawater chlorinity, but have lost considerable Mg, Na, K, sulfate, and 02, and have gained Ca, alkalinity, Si, NH3 and H2S. The loss of sulfate is due to anhydrite precipitation, as indicated by the d34S value of the remaining dissolved sulfate. The 87Sr/86Sr ratio has been lowered to 0.7086 for the 80°C water and 0.7078 for the 115°C water, whereas the Sr concentration is nearly unchanged. The changes in major element composition relative to seawater are also larger for the 115°C water, indicating that the basement formation water at this site probably varies in composition with depth. Based on their direction relative to seawater, the compositional changes for the 80 and 115°C waters do not complement the changes inferred for the altered rocks from Hole 504B, suggesting that the bulk composition of the altered rocks, like their mineralogy, is largely unrelated to the present thermal and alteration regime in the hole. The exact nature of the reacted seawaters cannot be determined yet, however. During its 2 yr. residence in the hole, the surface seawater remaining at the end of Leg 70 would have reacted with the wall rocks and exchanged with their interstitial formation waters by diffusion and possibly convection. How far these processes have proceeded is not yet certain, although calculations suggest that diffusion alone could have largely exchanged the surface seawater for interstitial water. The d18O of the samples is indistinguishable from seawater, however, and the d14C of the 80°C sample is similar to that of ocean bottom water. Although the interpretation of these species is ambiguous, that of tritium should not be. Tritium analyses, which are in progress, should clarify the nature of the reacted seawaters obtained from the hole.

Composition of phyllosilicates from hydrothermally altered basalts of DSDP Hole 83-504B, Costa Rica Rift, Pacific Ocean

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or olivine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from < 100 A to a few hundred A. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystallinity of saponite. By contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of A thick. The Si/(Si + A1) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe + Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+A1) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite ± mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.

(Table 2) Chemical composition of skeletons of scleractinian non-zooxanthelate corals

The first data on chemical composition of nonreef-building non-zooxanthellate deep-sea corals presented in this publication allow us to identify following tendencies manifested in the biomineralization process. Comparison of concentration levels of some chemical elements in scleractinian corals and ambient ocean waters suggests that corals do not accumulate K in the process of biomineralization and weakly accumulate Mg, whereas Ca, Sr, Si, Al, Ti, Mn, Zn, Cu, Cd, Pb, and Fe are concentrated in skeletons of corals with enrichment coefficients of 10**3 to 10**7. Correlations between components contained in the skeletons of scleractinian corals suggest that the source of Al, Si, Fe, and Ti in them is the clayey constituent of bottom sediments and zooplankton, while trace elements are likely accumulated via bioassimilation from seawater. Such elements as Mn, Sr, Pb, and Cd can structurally substitute Ca in calcite and aragonite. Variations in concentrations of the elements in coral skeletons depending on their habitat depths are fairly significant. As could be expected Ca and Mg concentrations are prone to decrease with depth (R = -0.55 and -0.51, respectively), which can possibly be caused by partial dissolution of carbonate skeletons with increasing depth, whereas the Sr/Ca ratio does not depend on depth.

Biogeochemistry measurements in a mesocosm experiment in the Bay of Hopavagen, Norway, in August 2012

The goal of this work has been to examine the influence of upper ocean food web structure and functioning on both the natural and artificially enhanced sequestration of carbon within the ocean. Data obtained in the mesocosm experiment run in the Bay of Hopavågen in August 2012 are used to assess the extent to which organic matter produced within four different food webs is retained in the upper ocean food web versus remineralized back to carbon dioxide and inorganic nutrients (ammonium, dissolved silicon, phosphate) versus exported from the system in the form of rapidly sinking particles. The experiment was carried out in a set of 12 mesocosms covering, in triplicate, 2 different phytoplankton communities (diatom versus non-diatom) exposed to 2 different zooplankton communities (-copepod and +copepod). These starting conditions were established by first filling the bags, roughly simultaneously, with seawater from the Bay of Hopavågen. Mesozooplankton were then removed to the most complete extent possible immediately removed from half of the mesocosms through repeated vertical hauls of a plankton net (200 µm mesh). Nitrate and phosphate was added to half mesocosms daily to promote the growth of non-siliceous phytoplankton (e.g. dinoflagellates or coccolithophores). To the other half of the mesocosms, nitrate, phosphate, and silicate were added to promote the growth of diatoms. Material was allowed to settle and the two distinct phytoplankton populations were allowed to develop for 4 days, after which copepods collected from the Bay of Hopavågen were added back to the half of the N+P mesocosms and to the half of the N+P+Si mesocosms from which mesozooplankton had not been removed at the beginning. This yielded a set of four initial starting conditions (N+P-copepods, N+P+copepods, N+P+Si-copepods, and N+P+Si+copepods). In the primary mesocosms, samples for a set of core parameters were taken every time the mesocosms were sampled. Samples for particulates (PIC, BSi, POC, PON) were collected on GF/F or 0.4 µm polycarbonate.

Effects of high CO2 levels on the ecophysiology of the diatom Thalassiosira weissflogii differ depending on the iron nutritional status

Iron availability in seawater, namely the concentration of dissolved inorganic iron ([Fe']), is affected by changes in pH. Such changes in the availability of iron should be taken into account when investigating the effects of ocean acidification on phytoplankton ecophysiology because iron plays a key role in phytoplankton metabolism. However, changes in iron availability in response to changes in ocean acidity are difficult to quantify specifically using natural seawater because these factors change simultaneously. In the present study, the availability of iron and carbonate chemistry were manipulated individually and simultaneously in the laboratory to examine the effect of each factor on phytoplankton ecophysiology. The effects of various pCO2 conditions (390, 600, and 800 µatm) on the growth, cell size, and elemental stoichiometry (carbon [C], nitrogen [N], phosphorus [P], and silicon [Si]) of the diatom Thalassiosira weissflogii under high iron ([Fe'] = 240 pmol/l) and low iron ([Fe'] = 24 pmol/l) conditions were investigated. Cell volume decreased with increasing pCO2, whereas intracellular C, N, and P concentrations increased with increasing pCO2 only under high iron conditions. Si:C, Si:N, and Si:P ratios decreased with increasing pCO2. It reflects higher production of net C, N, and P with no corresponding change in net Si production under high pCO2 and high iron conditions. In contrast, significant linear relationships between measured parameters and pCO2 were rarely detected under low iron conditions. We conclude that the increasing CO2 levels could affect on the biogeochemical cycling of bioelements selectively under the iron-replete conditions in the coastal ecosystems.

Upper bound on neutrino mass based on T2K neutrino timing measurements

The Tokai to Kamioka (T2K) long-baseline neutrino experiment consists of a muon neutrino beam, produced at the J-PARC accelerator, a near detector complex and a large 295 km distant far detector. The present work utilizes the T2K event timing measurements at the near and far detectors to study neutrino time of flight as function of derived neutrino energy. Under the assumption of a relativistic relation between energy and time of flight, constraints on the neutrino rest mass can be derived. The sub-GeV neutrino beam in conjunction with timing precision of order tens of ns provide sensitivity to neutrino mass in the few MeV/c^2 range. We study the distribution of relative arrival times of muon and electron neutrino candidate events at the T2K far detector as a function of neutrino energy. The 90% C.L. upper limit on the mixture of neutrino mass eigenstates represented in the data sample is found to be m^2 < 5.6 MeV^2/c^4.

Aspectos metodológicos para la evaluación de sistemas de tomografía por emisión de positrones empleando técnicas Montecarlo, protocolos estandarizados y diferentes trazadores

Esta tesis analiza los elementos que afectan a la evaluación del rendimiento dentro de la técnica de radiodiagnóstico mediante tomografía por emisión de positrones (PET), centrándose en escáneres preclínicos. Se exploran las posibilidades de los protocolos estándar de evaluación sobre los siguientes aspectos: su uso como herramienta para validar programas de simulación Montecarlo, como método para la comparación de escáneres y su validez en el estudio del efecto sobre la calidad de imagen al utilizar radioisótopos alternativos. Inicialmente se estudian los métodos de evaluación orientados a la validación de simulaciones PET, para ello se presenta el programa GAMOS como entorno de simulación y se muestran los resultados de su validación basada en el estándar NEMA NU 4-2008 para escáneres preclínicos. Esta validación se ha realizado mediante la comparación de los resultados simulados frente a adquisiciones reales en el equipo ClearPET, describiendo la metodología de evaluación y selección de los parámetros NEMA. En este apartado también se mencionan las aportaciones desarrolladas en GAMOS para aplicaciones PET, como la inclusión de herramientas para la reconstrucción de imágenes. Por otro lado, la evaluación NEMA del ClearPET es utilizada para comparar su rendimiento frente a otro escáner preclínico: el sistema rPET-1. Esto supone la primera caracterización NEMA NU 4 completa de ambos equipos; al mismo tiempo que se analiza cómo afectan las importantes diferencias de diseño entre ellos, especialmente el tamaño axial del campo de visión y la configuración de los detectores. El 68Ga es uno de los radioisótopos no convencionales en imagen PET que está experimentando un mayor desarrollo, sin embargo, presenta la desventaja del amplio rango o distancia recorrida por el positrón emitido. Además del rango del positrón, otra propiedad física característica de los radioisótopos PET que puede afectar a la imagen es la emisión de fotones gamma adicionales, tal como le ocurre al isótopo 48V. En esta tesis se evalúan dichos efectos mediante estudios de resolución espacial y calidad de imagen NEMA. Finalmente, se analiza el alcance del protocolo NEMA NU 4-2008 cuando se utiliza para este propósito, adaptándolo a tal fin y proponiendo posibles modificaciones. Abstract This thesis analyzes the factors affecting the performance evaluation in positron emission tomography (PET) imaging, focusing on preclinical scanners. It explores the possibilities of standard protocols of assessment on the following aspects: their use as tools to validate Monte Carlo simulation programs, their usefulness as a method for comparing scanners and their validity in the study of the effect of alternative radioisotopes on image quality. Initially we study the methods of performance evaluation oriented to validate PET simulations. For this we present the GAMOS program as a simulation framework and show the results of its validation based on the standard NEMA NU 4-2008 for preclinical PET scanners. This has been accomplished by comparing simulated results against experimental acquisitions in the ClearPET scanner, describing the methodology for the evaluation and selection of NEMA parameters. This section also mentions the contributions developed in GAMOS for PET applications, such as the inclusion of tools for image reconstruction. Furthermore, the evaluation of the ClearPET scanner is used to compare its performance against another preclinical scanner, specifically the rPET-1 system. This is the first complete NEMA NU 4 based characterization study of both systems. At the same time we analyze how do the significant design differences of these two systems, especially the size of the axial field of view and the detectors configuration affect their performance characteristics. 68Ga is one of the unconventional radioisotopes in PET imaging the use of which is currently significantly increasing; however, it presents the disadvantage of the long positron range (distance traveled by the emitted positron before annihilating with an electron). Besides the positron range, additional gamma photon emission is another physical property characteristic of PET radioisotopes that can affect the reconstructed image quality, as it happens to the isotope 48V. In this thesis we assess these effects through studies of spatial resolution and image quality. Finally, we analyze the scope of the NEMA NU 4-2008 to carry out such studies, adapting it and proposing possible modifications.

Self-assembled MgxZn1−xO quantum dots (0 ≤ x ≤ 1) on different substrates using spray pyrolysis methodology

By using the spray pyrolysis methodology in its classical configuration we have grown self-assembled MgxZn1−xO quantum dots (size [similar]4–6 nm) in the overall range of compositions 0 ≤ x ≤ 1 on c-sapphire, Si (100) and quartz substrates. Composition of the quantum dots was determined by means of transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy. Selected area electron diffraction reveals the growth of single phase hexagonal MgxZn1−xO quantum dots with composition 0 ≤ x ≤ 0.32 by using a nominal concentration of Mg in the range 0 to 45%. Onset of Mg concentration about 50% (nominal) forces the hexagonal lattice to undergo a phase transition from hexagonal to a cubic structure which resulted in the growth of hexagonal and cubic phases of MgxZn1−xO in the intermediate range of Mg concentrations 50 to 85% (0.39 ≤ x ≤ 0.77), whereas higher nominal concentration of Mg ≥ 90% (0.81 ≤ x ≤ 1) leads to the growth of single phase cubic MgxZn1−xO quantum dots. High resolution transmission electron microscopy and fast Fourier transform confirm the results and show clearly distinguishable hexagonal and cubic crystal structures of the respective quantum dots. A difference of 0.24 eV was detected between the core levels (Zn 2p and Mg 1s) measured in quantum dots with hexagonal and cubic structures by X-ray photoemission. The shift of these core levels can be explained in the frame of the different coordination of cations in the hexagonal and cubic configurations. Finally, the optical absorption measurements performed on single phase hexagonal MgxZn1−xO QDs exhibited a clear shift in optical energy gap on increasing the Mg concentration from 0 to 40%, which is explained as an effect of substitution of Zn2+ by Mg2+ in the ZnO lattice.