<div>Inorganic metal chalcogenide materials are of great importance in the semiconducting field for various electronic applications such as photovoltaics, thermoelectrics, sensors, and many others. Compared to traditional vacuum processing routes, solution processing provides an alternate cost-effective route to synthesize these inorganic materials through its ease of synthesis and device fabrication, higher material utilization, mild processing conditions, and opportunity for roll-to-roll manufacturing. One such versatile solution chemistry involving a mixture of amine and thiol species has evolved in the past few years as a common solvent for various precursor dissolutions including metal salts, metal oxides, elemental metals, and chalcogens.</div><div><br></div><div>The amine-thiol solvent system has been used by various researchers for the fabrication of inorganic materials, but without the complete understanding of the chemistry involved in this system, utilizing its full potential, and overcoming any inherent limitations will be difficult. So, to identify the organometallic complexes and their reaction pathways, the precursor dissolutions in amine-thiol solutions, specifically for elemental metals like Cu, In and chalcogens like Se, Te were studied using X-ray absorption, nuclear magnetic resonance, infrared, and Raman spectroscopy along with electrospray ionization mass spectrometry techniques. These analyses suggested the formation of metal thiolate complexes in the solution with the release of hydrogen gas in the case of metal dissolutions confirming irreversibility of the dissolution. Insights gained for chalcogen dissolutions confirmed the formation of different species like monoatomic or polyatomic clusters when different amine-thiol pair is used for dissolution. Results from these analyses also identified the role of each component in the dissolution which allowed for tuning of the solutions by isolating the complexes to reduce their reactivity and corrosivity for commercial applications.</div><div><br></div><div>After identifying complexes in metal dissolution for Cu and In metals, the decomposition pathway for these complexes was studied using X-ray diffraction and gas chromatography mass spectrometry techniques which confirmed the formation of phase pure metal chalcogenide material with a release of volatile byproducts like hydrogen sulfide and thiirane. This allowed for the fabrication of impurity-free thin-film Cu(In,Ga)S2 material for use in photovoltaic applications. The film fabrication with reduced carbon impurity achieved using this solvent system yielded a preliminary promising efficiency beyond 12% for heavy alkali-free, low bandgap CuInSe2 material. Along with promising devices, by utilizing the understanding of the chalcogen complexation, a new method for CuInSe2 film fabrication was developed with the addition of selenide precursors and elemental selenium which enabled first-ever fabrication of a solution-processed CuInSe2 thin film with thickness above 2 μm and absence of any secondary fine-grain layer.</div><div><br></div><div>Along with thin-film fabrication, a room temperature synthesis route for lead chalcogenide materials (PbS, PbSe, PbTe) with controlled size, shape, crystallinity, and composition of nanoparticle self-assemblies was demonstrated. Micro-assemblies formed via this route, especially the ones with hollow-core morphology were subjected to a solution-based anion and cation exchange to introduced desired foreign elements suitable for improving the thermoelectric properties of the material. Adopting from traditional hot injection and heat up synthesis routes, a versatile synthesis procedure for various binary, ternary, and quaternary metal chalcogenide (sulfide and sulfoselenide) nanoparticles from elemental metals like Cu, Zn, Sn, In, Ga, and Se was developed. This new synthesis avoids the incorporation of impurities like O, Cl, I, Br arising from a traditional metal oxide, halide, acetate, or other similar metal salt precursors giving an opportunity for truly impurity-free colloidal metal chalcogenide nanoparticle synthesis.</div>

<div>Increasing flexibility of light manipulation is vital for various domains including both biomedical and military applications, where a lack of photon control could become critical. The efforts conducted and projected within this proposal are focused on three major areas: semi-continuous planar thin film photomodification for infrared (IR) filtering, nanosphere core-shell structures for obscurance, and all-dielectric sub-wavelength focal lenses for advanced IR sensing.Through a collaborative effort with the Army Research Office, we advanced the tunability of planar plasmonic filters with cutoff wavelengths in the 10–16μm range with photomodification using a 10.6μm CO2laser. Surface-enhanced molecular absorption in concert with three-dimensional (3D) Au nano-structures with inherent broad absorption in the IR band was a novel approach utilized to create such planar filters.Expanding on these, efforts and the results of the 2-dimensional (2D) semicontinuous Au plasmonic planar filtering, we further advanced our research with 3D Au nano-coreshell structures to enable levitated long-wavelength pass filter obscurants. We exploited the radiative effects of Au nano-structures that mimic conventional apertures or antennas, though these structures are on the nanometer scale and demonstrated the filtering characteristics through flow cell.In parallel with our plasmonic filtering we designed, manufactured and tested low loss dielectric microlenses for IR radiation based on a dielectric metasurface layer by patterning a SI substrate and etching to sub-micron depths. For a proof-of-concept lens demonstration,we chose a fine patterned array of nano-pillars with variable diameters.Merging our plasmonic filtering and dielectric microlens efforts, we created a holographic lenslet by designing and simulating a low loss focusing metasurface lens with engineered nano-scaled features to converge off-axis IR radiation. An array of nano-pillars with varied diameter and fixed height and periodicity was chosen for ease of fabrication with single layer etching</div>

Solution-processed lead sulfide quantum dots (PbS QDs) are an excellent candidate for photodetector applications because they exhibit broadband absorption, a wide range of tuneable bandgaps, high stability in air, and mechanical flexibility. However, a crucial criterion for the fabrication of high-performance photodetectors is the selection of the ligands, which can facilitate charge carrier transport between the PbS QDs and passivate the surface defects. In this work, the authors have studied the effect of traps on the performance of PbS QD photodetectors that are fabricated using different types of ligands, using intensity-dependent photoresponse dynamics. The best devices with lead halide ligands show a dark current density of 5 × 10−9 A cm−2 at −0.2 V, which is one of the lowest values reported thus far for solution-processed PbS QD-based photodetectors. Moreover, these devices show a high linear dynamic range (≈90 dB) and high detectivity (>1013 Jones), in addition to an f-3 dB of greater than 100 kHz without the application of an external voltage bias at a wavelength of 784 nm. These results suggest that with an appropriate selection of ligands, solution-processed photodetectors with a lower density of traps and a better device performance can be fabricated.

[EN] Positron Emission Tomography (PET) is a non-invasive nuclear medical imaging modality that makes it possible to observe the distribution of metabolic substances within a patient's body after marking them with radioactive isotopes and arranging an annular scanner around him in order to detect their decays. The main applications of this technique are the detection and tracing of tumors in cancer patients and metabolic studies with small animals. The Electronic Design for Nuclear Applications (EDNA) research group within the Instituto de Instrumentación para Imagen Molecular (I3M) has been involved in the study of high performance PET systems and maintains a small experimental setup with two detector modules. This thesis is framed within the necessity of developing a new data acquisition system (DAQ) for the aforementioned setup that corrects the drawbacks of the existing one. The main objective is to define a DAQ architecture that is completely scalable, modular, and guarantees the mobility and the possibility of reusing its components, so that it admits any extension of modification of the setup and it is possible to export it directly to the configurations used by other groups or experiments. At the same time, this architecture should be compatible with the best possible resolutions attainable at the present instead of imposing artificial limits on system performance. In particular, the new DAQ system should outperform the previous one. As a first step, a general study of DAQ arquitectures is carried out in the context of experimental setups for PET and other high energy physics applications. On one hand, the conclusion is reached that the desired specifications require early digitization of detector signals, exclusively digital communication between modules, and the absence of a centralized trigger. On the other hand, the necessity of a very precise distributed synchronization scheme between modules becomes apparent, with errors in the order of 100 ps, and operating directly over the data links. A study of the existing methods reveals their severe limitations in terms of achievable precision. A theoretical analysis of the situation is carried out with the goal of overcoming them, and a new synchronization algorithm is proposed that is able to reach the desired resolution while getting rid of the restrictions on clock alignment that are imposed by virtually all usual schemes. Since the measurement of clock phase difference plays a crucial role in the proposed algorithm, extensions to the existing methods are defined and analyzed that improve them significantly. The proposed scheme for synchronism is validated using commercial evaluation boards. Taking the proposed synchronization method as a starting point, a DAQ architecture for PET is defined that is composed of two types of module (acquisition and concentration) whose replication makes it possible to arrange a hierarchic system of arbitrary size, and circuit boards are designed and commissioned that implement a realization of the architecture for the particular case of two detectors. This DAQ is finally installed at the experimental setup, where their synchronization properties and resolution as a PET system are characterized and its performance is verified to have improved with respect to the previous system. / [ES] La Tomografía por Emisión de Positrones (PET) es una modalidad de imagen médica nuclear no invasiva que permite observar la distribución de sustancias metabólicas en el interior del cuerpo de un paciente tras marcarlas con isótopos radioactivos y disponer después un escáner anular a su alrededor para detectar su desintegración. Las principales aplicaciones de esta técnica son la detección y seguimiento de tumores en pacientes con cáncer y los estudios metabólicos en animales pequeños. El grupo de investigación Electronic Design for Nuclear Applications (EDNA) del Instituto de Instrumentación para Imagen Molecular (I3M) ha estado involucrado en el estudio de sistemas PET de alto rendimiento y mantiene un pequeño setup experimental con dos módulos detectores. La presente tesis se enmarca dentro de la necesidad de desarrollar un nuevo sistema de adquisición de datos (DAQ) para dicho setup que corrija los inconvenientes del ya existente. En particular, el objetivo es definir una arquitectura de DAQ que sea totalmente escalable, modular, y que asegure la movilidad y la posibilidad de reutilización de sus componentes, de manera que admita cualquier ampliación o alteración del setup y pueda exportarse directamente a los de otros grupos o experimentos. Al mismo tiempo, se desea que dicha arquitectura no limite artificialmente el rendimiento del sistema sino que sea compatible con las mejores resoluciones disponibles en la actualidad, y en particular que sus prestaciones superen a las del DAQ instalado previamente. En primer lugar, se lleva a cabo un estudio general de las arquitecturas de DAQ para setups experimentales para PET y otras aplicaciones de física de altas energías. Por un lado, se determina que las características deseadas implican la digitalización temprana de las señales del detector, la comunicación exclusivamente digital entre módulos, y la ausencia de trigger centralizado. Por otro lado, se hace patente la necesidad de un esquema de sincronización distribuida muy preciso entre módulos, con errores del orden de 100 ps, que opere directamente sobre los enlaces de datos. Un estudio de los métodos ya existentes revela sus graves limitaciones a la hora de alcanzar esas precisiones. Con el fin de paliarlos, se lleva a cabo un análisis teórico de la situación y se propone un nuevo algoritmo de sincronización que es capaz de alcanzar la resolución deseada y elimina las restricciones de alineamiento de reloj impuestas por casi todos los esquemas usuales. Dado que la medida de desfase entre relojes juega un papel crucial en el algoritmo propuesto, se definen y analizan extensiones a los métodos ya existentes que suponen una mejora sustancial. El esquema de sincronismo propuesto se valida utilizando placas de evaluación comerciales. Partiendo del método de sincronismo propuesto, se define una arquitectura de DAQ para PET compuesta de dos tipos de módulos (adquisición y concentración) cuya replicación permite construir un sistema jerárquico de tamaño arbitrario, y se diseñan e implementan placas de circuito basadas en dicha arquitectura para el caso particular de dos detectores. El DAQ así construído se instala finalmente en el setup experimental, donde se caracterizan tanto sus propiedades de sincronización como su resolución como sistema PET y se comprueba que sus prestaciones son superiores a las del sistema previo. / [CA] La Tomografia per Emissió de Positrons (PET) és una modalitat d'imatge mèdica nuclear no invasiva que permet observar la distribució de substàncies metabòliques a l'interior del cos d'un pacient després d'haver-les marcat amb isòtops radioactius disposant un escàner anular al seu voltant per a detectar la seua desintegració. Aquesta tècnica troba les seues principals aplicacions a la detecció i seguiment de tumors a pacients amb càncer i als estudis metabòlics en animals petits. El grup d'investigació Electronic Design for Nuclear Applications (EDNA) de l'Instituto de Instrumentación para Imagen Molecular (I3M) ha estat involucrat en l'estudi de sistemes PET d'alt rendiment i manté un petit setup experimental amb dos mòduls detectors. Aquesta tesi neix de la necessitat de desenvolupar un nou sistema d'adquisició de dades (DAQ) per al setup esmentat que corregisca els inconvenients de l'anterior. En particular, l'objectiu és definir una arquitectura de DAQ que sigui totalment escalable, modular, i que asseguri la mobilitat i la possibilitat de reutilització dels seus components, de tal manera que admeta qualsevol ampliació o alteració del setup i pugui exportar-se directament a aquells d'altres grups o experiments. Al mateix temps, es desitja que aquesta arquitectura no introduisca límits artificials al rendiment del sistema sinó que sigui compatible amb les millors resolucions disponibles a l'actualitat, i en particular que les seues prestacions siguin superiors a les del DAQ instal.lat amb anterioritat. En primer lloc, es porta a terme un estudi general de les arquitectures de DAQ per a setups experimentals per a PET i altres aplicacions de física d'altes energies. Per una banda, s'arriba a la conclusió que les característiques desitjades impliquen la digitalització dels senyals del detector el més aviat possible, la comunicació exclusivament digital entre mòduls, i l'absència de trigger centralitzat. D'altra banda, es fa palesa la necessitat d'un mecanisme de sincronització distribuïda molt precís entre mòduls, amb errors de l'ordre de 100 ps, que treballi directament sobre els enllaços de dades. Un estudi dels mètodes ja existents revela les seues greus limitacions a l'hora d'assolir aquest nivell de precisió. Amb l'objectiu de pal.liar-les, es duu a terme una anàlisi teòrica de la situació i es proposa un nou algoritme de sincronització que és capaç d'obtindre la resolució desitjada i es desfà de les restriccions d'alineament de rellotges imposades per gairebé tots els esquemes usuals. Atès que la mesura del desfasament entre rellotges juga un paper cabdal a l'algoritme proposat, es defineixen i analitzen extensions als mètodes ja existents que suposen una millora substancial. L'esquema de sincronisme proposat es valida mitjançant plaques d'avaluació comercials. Prenent el mètode proposat com a punt de partida, es defineix una arquitectura de DAQ per a PET composta de dos tipus de mòduls (d'adquisició i de concentració) tals que la replicació d'aquests elements permet construir un sistema jeràrquic de mida arbitrària, i es dissenyen i implementen plaques de circuit basades en aquesta arquitectura per al cas particular de dos detectors. L'electrònica desenvolupada s'instal.la finalment al setup experimental, on es caracteritzen tant les seues propietats de sincronització com la seua resolució com a sistema PET i es comprova que les seues prestacions són superiors a les del sistema previ. / Aliaga Varea, RJ. (2016). Development of a data acquisition architecture with distributed synchronization for a Positron Emission Tomography system with integrated front-end [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63271 / Premios Extraordinarios de tesis doctorales

<p>The last two decades have shown a boom in the field of wearable sensing technology. Particularly in the consumer industry, growing trends towards personalized health have pushed new devices to report many vital signs, with a demand for high accuracy and reliability. The most common technique used to gather these vitals is photoplethysmography or PPG. PPG devices are ideal for wearable applications as they are simple, power-efficient, and can be implemented on almost any area of the body. Traditionally PPGs were utilized for capturing just heart rate, however, recent advancements in hardware and digital processing have led to other metrics including respiratory rate (RR) and peripheral oxygen saturation (SpO2), to be reported as well. Our research investigates the potential for wearable devices to be used for outpatient apnea monitoring, and particularly the ability to detect opioid misuse resulting in respiratory depression. Ultimately, the long-term goal of this work is to develop a wearable device that can be used in the rehabilitation process to ensure both accountability and safety of the wearer. This document details contributions towards this goal through the design, development, and evaluation of a device called “Kick Ring”. Primarily, we investigate the ability of Kick Ring to record heartrate (HR), RR, and SpO2. Moreover, we show that the device can calculate RR in real time and can provide an immediate indication of abnormal events such as respiratory depression. Finally, we explore a novel method for reporting apnea events through the use of several PPG characteristics. Kick Ring reliably gathers respiratory metrics and offers a combination of features that does not exist in the current wearables space. These advancements will help to move the field forward, and eventually aid in early detection of life-threatening events.</p>