Molecular diagnostics is a fast growing field with new technologies being developed constantly. There is a demand for more sophisticated molecular tools able to detect a multitude of molecules on a single molecule level with high specificity, able to distinguish them from other similar molecules. This becomes very important for infectious diagnostics with the increasing antibiotic resistant viruses and bacteria, in gene based diagnostics and for early detection and more targeted treatments of cancer. For increased sensitivity, simplicity, speed and user friendliness, novel readouts are emerging, taking advantage of new technologies being discovered in the field of nanotechnology.  This thesis, based upon four papers, examines two novel electrical readouts for amplified single molecule detection. Target probing is based upon the highly specific amplification technique rolling circle amplification (RCA). RCA enables localized amplification resulting in a long single stranded DNA molecule containing tandem repeats of the probing sequence as product. Paper I demonstrates sensitive detection of bacterial genomic DNA using a magnetic nanoparticles-based substrate-free method where as few as 50 bacteria can be detected. Paper II illustrates a new sensor concept based on the formation of conducting molecular nanowires forming a low resistance circuit. The rolling circle products are stretched to bridge an electrode gap and upon metallization the resistance drops by several orders of magnitude, resulting in an extremely high signal to noise ratio. Paper III explores a novel metallization technique, demonstrating the efficient incorporation of boranephosphonate modified nucleotides during RCA.  In the presence of a silver ion solution, defined metal nanoparticles are formed along the DNA molecule with high spatial specificity. Paper IV demonstrates the ability to manipulate rolling circle products by dielectrophoresis. In the presence of a high AC electric field the rolling circle products stretch to bridge a 10 µm electrode gap.

A novel UHV microcalorimeter has been used to study the interaction between calcium and three polymers: MEH-PPV, MEH-PPP and P3HT. All three polymers behave differently in their reaction kinetics with calcium. On MEH-PPV we measure 45 μJ/cm² of heat generated in excess of the heat of bulk metal growth, 120 μJ/cm² for MEH-PPP, and 100 μJ/cm² for P3HT. Comparison of the MEH-PPV and MEHPPP data indicate that the initial reaction of calcium with MEH-PPV occurs at the vinylene group. We propose, based on hypothetical models, that calcium reacts with the vinylene groups of MEH-PPV with a reaction heat of 360 kJ/mol and at a projected surface density of 1.7 sites/nm², while it reacts with the phenylene groups of MEH-PPP in a two-step process with reaction heats of 200 and 360 kJ/mol respectively, at a projected surface density of 3.5 sites/nm². Optical absorption experiments, using either a 1.85 eV diode laser or a xenon lamp coupled to a scanning monochromator, have also been performed using the same calorimeter sensor. In the case of MEH-PPV, using the laser we find an optical absorption cross-section of 3E-¹⁷ cm² per incident calcium atom at low coverages. The change in absorptance at higher coverages correlates perfectly with the population of reacted Ca atoms determined calorimetrically. The size of the absorbance cross-section, and its position just within the band gap of the polymer, are consistent with the reaction being one of polaron formation. Calcium does not appear to dope P3HT, while the photon energy range of 1.5 to 3.75 eV used in these experiments is likely too small for probing polaronic energy states in MEH-PPP.

abstract: Non-volatile memory (NVM) has become a staple in the everyday life of consumers. NVM manifests inside cell phones, laptops, and most recently, wearable tech such as smart watches. NAND Flash has been an excellent solution to conditions requiring fast, compact NVM. Current technology nodes are nearing the physical limits of scaling, preventing flash from improving. To combat the limitations of flash and to appease consumer demand for progressively faster and denser NVM, new technologies are needed. One possible candidate for the replacement of NAND Flash is programmable metallization cells (PMC). PMC are a type of resistive memory, meaning that they do not rely on charge storage to maintain a logic state. Depending on their application, it is possible that devices containing NVM will be exposed to harsh radiation environments. As part of the process for developing a novel memory technology, it is important to characterize the effects irradiation has on the functionality of the devices. This thesis characterizes the effects that ionizing γ-ray irradiation has on the retention of the programmed resistive state of a PMC. The PMC devices tested used Ge30Se70 doped with Ag as the solid electrolyte layer and were fabricated by the thesis author in a Class 100 clean room. Individual device tiles were wire bonded into ceramic packages and tested in a biased and floating contact scenario. The first scenario presented shows that PMC devices are capable of retaining their programmed state up to the maximum exposed total ionizing dose (TID) of 3.1 Mrad(Si). In this first scenario, the contacts of the PMC devices were left floating during exposure. The second scenario tested shows that the PMC devices are capable of retaining their state until the maximum TID of 10.1 Mrad(Si) was reached. The contacts in the second scenario were biased, with a 50 mV read voltage applied to the anode contact. Analysis of the results show that Ge30Se70 PMC are ionizing radiation tolerant and can retain a programmed state to a higher TID than NAND Flash memory. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

abstract: This PhD thesis consists of three main themes. The first part focusses on modeling of Silver (Ag)-Chalcogenide glass based resistive memory devices known as the Programmable Metallization Cell (PMC). The proposed models are examined with the Technology Computer Aided Design (TCAD) simulations. In order to find a relationship between electrochemistry and carrier-trap statistics in chalcogenide glass films, an analytical mapping for electron trapping is derived. Then, a physical-based model is proposed in order to explain the dynamic behavior of the photodoping mechanism in lateral PMCs. At the end, in order to extract the time constant of ChG materials, a method which enables us to determine the carriers’ mobility with and without the UV light exposure is proposed. In order to validate these models, the results of TCAD simulations using Silvaco ATLAS are also presented in the study, which show good agreement. In the second theme of this dissertation, a new model is presented to predict single event transients in 1T-1R memory arrays as an inverter, where the PMC is modeled as a constant resistance while the OFF transistor is model as a diode in parallel to a capacitance. The model divides the output voltage transient response of an inverter into three time segments, where an ionizing particle striking through the drain–body junction of the OFF-state NMOS is represented as a photocurrent pulse. If this current source is large enough, the output voltage can drop to a negative voltage. In this model, the OFF-state NMOS is represented as the parallel combination of an ideal diode and the intrinsic capacitance of the drain–body junction, while a resistance represents an ON-state NMOS. The proposed model is verified by 3-D TCAD mixed-mode device simulations. In order to investigate the flexibility of the model, the effects of important parameters, such as ON-state PMOS resistance, doping concentration of p-region in the diode, and the photocurrent pulse are scrutinized. The third theme of this dissertation develops various models together with TCAD simulations to model the behavior of different diamond-based devices, including PIN diodes and bipolar junction transistors (BJTs). Diamond is a very attractive material for contemporary power semiconductor devices because of its excellent material properties, such as high breakdown voltage and superior thermal conductivity compared to other materials. Collectively, this research project enhances the development of high power and high temperature electronics using diamond-based semiconductors. During the fabrication process of diamond-based devices, structural defects particularly threading dislocations (TDs), may affect the device electrical properties, and models were developed to account of such defects. Recognition of their behavior helps us understand and predict the performance of diamond-based devices. Here, the electrical conductance through TD sites is shown to be governed by the Poole-Frenkel emission (PFE) for the temperature (T) range of 323 K ˂ T ˂ 423 K. Analytical models were performed to fit with experimental data over the aforementioned temperature range. Next, the Silvaco Atlas tool, a drift-diffusion based TCAD commercial software, was used to model diamond-based BJTs. Here, some field plate methods are proposed in order to decrease the surface electric field. The models used in Atlas are modified to account for both hopping transport in the impurity bands associated with high activation energies for boron doped and phosphorus doped diamond. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2017

abstract: The Programmable Metallization Cell (PMC) is a novel solid-state resistive switching technology. It has a simple metal-insulator-metal “MIM” structure with one metal being electrochemically active (Cu) and the other one being inert (Pt or W), an insulating film (silica) acts as solid electrolyte for ion transport is sandwiched between these two electrodes. PMC’s resistance can be altered by an external electrical stimulus. The change of resistance is attributed to the formation or dissolution of Cu metal filament(s) within the silica layer which is associated with electrochemical redox reactions and ion transportation. In this dissertation, a comprehensive study of microfabrication method and its impacts on performance of PMC device is demonstrated, gamma-ray total ionizing dose (TID) impacts on device reliability is investigated, and the materials properties of doped/undoped silica switching layers are illuminated by impedance spectroscopy (IS). Due to the inherent CMOS compatibility, Cu-silica PMCs have great potential to be adopted in many emerging technologies, such as non-volatile storage cells and selector cells in ultra-dense 3D crosspoint memories, as well as electronic synapses in brain-inspired neuromorphic computing. Cu-silica PMC device performance for these applications is also assessed in this dissertation. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2017

[pt] O presente trabalho, aborda o estudo fenomenológico da metalização de briquetes auto-redutores durante a reação de redução na faixa de temperatura de 1000 à 1350 graus Celsius, variando o tipo de atmosfera gasosa e o tempo de redução. Com base nos resultados obtidos, uma descrição das morfologias do ferro presentes na faixa de temperatura estudada são apresentadas. Para tanto foram utilizados: estereoscópios, microscópios óticos e eletrônico. As principais morfologias da fase metálica reduzida foram: a presença de glóbulos de ferro no interior do aglomerado e uma camada contínua de ferro metálico na superfície, entre 1200 - 1350 graus Celsius, sugerindo uma carbonetação mais intensa no interior, com a conseqüente fusão da fase metálica. Crescimento de whiskers de ferro, também foram observados nas temperaturas mais baixas (1000 - 1100 graus Celsius). Na revisão bibliográfica foram feitos comentários sobre as tecnologias atuais e emergentes de produção de ferro primário e aço, e evidenciada a importância do estudo morfológico no esclarecimento do complexo mecanismo da cinética de redução de misturas de minério de ferro e carbono. Uma abordagem termodinâmica e cinética destes estudos também foi apresentada. / [en] This work describes the morphological study of the metallization process of self-reducing briquettes containing fines of iron ore and coal. The reduction of briquettes was effected in a temperature range of 1.000 to 1.350 Degrees Celsius varying reduction process duration and the gas atmosphere with nitrogen, carbon monoxide and carbon dioxide. The different phases of the morphology of the metallic iron were measured by the use of stereoscopic devices as well as optical and scanning electron microscopes. The main morphology occurred in a temperature range of 1.200 to 1.350 Degrees Celsius generating iron globules in the center of the briquettes and a continuous metallic layer on the surface. The presence of a dendritic structure and the high carbon content of the iron globules indicate that the highest intensity of carburization occurred in the core regions of the briquettes followed by the melting phase of the iron. The whisker growth of iron was observed in the lower temperature range of 1.000 to 1.100 Degrees Celsius. The bibliographic section makes references to the actual status and new developments in the research of processes based on composite iron ore agglomerates. It is common understanding that the iron morphology plays a key role in the kinetic mechanisms of reducing iron oxide and carbon mixtures.

abstract: Nonvolatile memory (NVM) technologies have been an integral part of electronic systems for the past 30 years. The ideal non-volatile memory have minimal physical size, energy usage, and cost while having maximal speed, capacity, retention time, and radiation hardness. A promising candidate for next-generation memory is ion-conducting bridging RAM which is referred to as programmable metallization cell (PMC), conductive bridge RAM (CBRAM), or electrochemical metallization memory (ECM), which is likely to surpass flash memory in all the ideal memory characteristics. A comprehensive physics-based model is needed to completely understand PMC operation and assist in design optimization. To advance the PMC modeling effort, this thesis presents a precise physical model parameterizing materials associated with both ion-rich and ion-poor layers of the PMC's solid electrolyte, so that captures the static electrical behavior of the PMC in both its low-resistance on-state (LRS) and high resistance off-state (HRS). The experimental data is measured from a chalcogenide glass PMC designed and manufactured at ASU. The static on- and off-state resistance of a PMC device composed of a layered (Ag-rich/Ag-poor) Ge30Se70 ChG film is characterized and modeled using three dimensional simulation code written in Silvaco Atlas finite element analysis software. Calibrating the model to experimental data enables the extraction of device parameters such as material bandgaps, workfunctions, density of states, carrier mobilities, dielectric constants, and affinities. The sensitivity of our modeled PMC to the variation of its prominent achieved material parameters is examined on the HRS and LRS impedance behavior. The obtained accurate set of material parameters for both Ag-rich and Ag-poor ChG systems and process variation verification on electrical characteristics enables greater fidelity in PMC device simulation, which significantly enhances our ability to understand the underlying physics of ChG-based resistive switching memory. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2014

Le travail de thèse a consisté à développer des voies originales de microfabrication pour laconception d’électrodes qui pourront être utilisées dans un biocapteur basé sur unetransduction électrochimique. Une des perspectives étant de pouvoir intégrer ce type decapteur dans un microsystème analytique à base microfluidique, nous avons fait le choix duverre comme matériau de base. Par ailleurs, nous avons privilégié les technologies de« lithographie douce » au détriment de voies classiques telles que la photolithographie afin derendre inutile l’accès à des salles à environnement contrôlé ou l’utilisation d’appareillagessophistiqués.Lors de ce travail, nous avons plus particulièrement travaillé sur le développement deméthodes combinant la technique de microtamponnage et la métallisation chimique de typeautocatalytique (electroless). Cette métallisation nécessitant des surfaces catalytiques pourfaire croître la couche métallique, nous avons développé des méthodes de traitements desurface afin de rendre le substrat de base catalytique sur toute sa surface. La technique demicrotamponnage a ensuite été utilisée afin de passiver les zones où la métallisation n’est pasdésirée et cela a mené à des microstructures métalliques en surface du verre présentant peu oupas de défauts. Notre approche nous a conduit à utiliser plusieurs types de catalyseurs sous laforme de nanoparticules métalliques à base d’argent, d’or ou de palladium et nous avonsdiscuté les différences entre les méthodes basées sur ces différents catalyseurs.Une autre voie a consisté à graver de façon localisée des couches minces métalliquesuniformes en protégeant les zones ne devant pas être gravées par la technique demicrotamponnage. Ceci a permis le développement de deux voies originales demicrostructuration sur couches minces métalliques uniformes (d’une part le pelage sélectif etd’autre part le procédé à double inversion).Dans l’ensemble de nos travaux, des caractérisations d’extrême surface par les techniquesSEM, AFM, ToF-SIMS, XPS et de mouillabilité ont été menées afin d’optimiser ledéveloppement des différents procédés. / This thesis work consisted in the development of original strategy for the microfabrication ofelectrodes which could be used in a biosensor as an electrochemical transducer. One of theprospects of this work is to insert this type of sensor into a microfluidic chip, We have madethe choice of using glass as a substrate. Moreover, we have favoured soft lithographictechnologies at the expense of conventional strategy like photolithography.In this work, we mainly worked on the development of methods which combines microcontact printing and autocatalytic metallisation (electroless). As this type of metallisationneeds catalytic surfaces to grow the metallic layer, we developed surface treatments methodsto make the surface of the substrate catalytic for the metallisation. To follow, the microcontact printing technique has been used to passivate areas where metallisation should notoccur and this leads to metallic microstructure with very few defects. Our approach leads uson the use of different catalyst like gold, silver or palladium nanoparticles and we havediscussed differences between the different methods.Another strategy consisted in the selective etching of thin metallic layer. Areas not to be etchare protected by the micro contact printing technique. This leads to the development of twooriginal strategies of microfabrication on thin metallic layer.In the whole work, extreme surface characterisation like SEM, AFM, ToF-SIMS, XPS andwettability have been carried out in order to optimize the development of the differentmethods.

Abstract While numerous publications deal with the properties and applications of porous silicon (PS), some of the related topics are not complete or could be investigated from different aspects. Therefore, the main objective of this thesis is to provide novel information associated with the optical and chemical properties of PS. For the investigations, various PS samples are manufactured by electrochemical dark etching of boron-doped p+-type Si wafers. Amongst others, (i) the wavelength-dependent refractive indices of freestanding PS monolayers having different porosities were obtained from optical transmission and reflection spectra in the 700–1700 nm wavelength range, and compared to those calculated from Bruggeman's effective medium approximation (EMA). The refractive indices of the PS samples are shown to be described well with the EMA. In addition, optical scattering at the air-PS interface was demonstrated. (ii) Multilayer stacks are created by alternating the porosities of PS layers within the same sample to form Bragg filters. The Bragg conditions of the filters are calculated and compared to optical transmission measurements. (iii) The oxidation of PS membranes in dry air is investigated with emphases on the reaction kinetics and on the structural changes of the porous matter. As revealed, oxidation proceeds faster in PS than in Si bulk. The formed SiO2 is amorphous and causes stress in the lattice of the residual Si skeleton. (iv) The effect of oxidation extent of PS layers on the growth mechanism of multi-walled carbon nanotubes (CNTs) is investigated. The density of the CNT network is found proportional to the oxidation extent of the substrates. (v) Finally, the chemically-reductive nature of PS is studied and exploited via the immersion plating method to deposit palladium and silver nanoparticles in the nanopores and on the surface of PS samples. The presented novel results have potential in silicon-based technologies, including integrated active and passive optical components (waveguides, filters, antireflection coatings, optical gas/liquid sensors), electronic devices (electrochemical gas/liquid sensors, diodes, field effect devices) and selective chemical catalysis (substrates, growth templates).

A novel UHV microcalorimeter has been used to study the interaction between calcium and three polymers: MEH-PPV, MEH-PPP and P3HT. All three polymers behave differently in their reaction kinetics with calcium. On MEH-PPV we measure 45 μJ/cm² of heat generated in excess of the heat of bulk metal growth, 120 μJ/cm² for MEH-PPP, and 100 μJ/cm² for P3HT. Comparison of the MEH-PPV and MEHPPP data indicate that the initial reaction of calcium with MEH-PPV occurs at the vinylene group. We propose, based on hypothetical models, that calcium reacts with the vinylene groups of MEH-PPV with a reaction heat of 360 kJ/mol and at a projected surface density of 1.7 sites/nm², while it reacts with the phenylene groups of MEH-PPP in a two-step process with reaction heats of 200 and 360 kJ/mol respectively, at a projected surface density of 3.5 sites/nm². Optical absorption experiments, using either a 1.85 eV diode laser or a xenon lamp coupled to a scanning monochromator, have also been performed using the same calorimeter sensor. In the case of MEH-PPV, using the laser we find an optical absorption cross-section of 3E-¹⁷ cm² per incident calcium atom at low coverages. The change in absorptance at higher coverages correlates perfectly with the population of reacted Ca atoms determined calorimetrically. The size of the absorbance cross-section, and its position just within the band gap of the polymer, are consistent with the reaction being one of polaron formation. Calcium does not appear to dope P3HT, while the photon energy range of 1.5 to 3.75 eV used in these experiments is likely too small for probing polaronic energy states in MEH-PPP. / Science, Faculty of / Chemistry, Department of / Graduate