This dissertation describes the development of a label-free, electrochemical immunosensing platform integrated into a low-cost microfluidic system for the sensitive, selective and accurate detection of cortisol, a steroid hormone co-related with many physiological disorders. Abnormal levels of cortisol is indicative of conditions such as Cushing’s syndrome, Addison’s disease, adrenal insufficiencies and more recently post-traumatic stress disorder (PTSD). Electrochemical detection of immuno-complex formation is utilized for the sensitive detection of Cortisol using Anti-Cortisol antibodies immobilized on sensing electrodes. Electrochemical detection techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) have been utilized for the characterization and sensing of the label-free detection of Cortisol. The utilization of nanomaterial’s as the immobilizing matrix for Anti-cortisol antibodies that leads to improved sensor response has been explored. A hybrid nano-composite of Polyanaline-Ag/AgO film has been fabricated onto Au substrate using electrophoretic deposition for the preparation of electrochemical immunosening of cortisol. Using a conventional 3-electrode electrochemical cell, a linear sensing range of 1pM to 1µM at a sensitivity of 66µA/M and detection limit of 0.64pg/mL has been demonstrated for detection of cortisol. Alternately, a self-assembled monolayer (SAM) of dithiobis(succinimidylpropionte) (DTSP) has been fabricated for the modification of sensing electrode to immobilize with Anti-Cortisol antibodies. To increase the sensitivity at lower detection limit and to develop a point-of-care sensing platform, the DTSP-SAM has been fabricated on micromachined interdigitated microelectrodes (µIDE). Detection of cortisol is demonstrated at a sensitivity of 20.7µA/M and detection limit of 10pg/mL for a linear sensing range of 10pM to 200nM using the µIDE’s. A simple, low-cost microfluidic system is designed using low-temperature co-fired ceramics (LTCC) technology for the integration of the electrochemical cortisol immunosensor and automation of the immunoassay. For the first time, the non-specific adsorption of analyte on LTCC has been characterized for microfluidic applications. The design, fabrication technique and fluidic characterization of the immunoassay are presented. The DTSP-SAM based electrochemical immunosensor on µIDE is integrated into the LTCC microfluidic system and cortisol detection is achieved in the microfluidic system in a fully automated assay. The fully automated microfluidic immunosensor hold great promise for accurate, sensitive detection of cortisol in point-of-care applications.

The Terahertz (1012 Hz) region of the electromagnetic spectrum covers the frequency range from roughly 300 GHz to 10 THz, which is in between the microwave and infrared regimes. The increasing interest in the development of ultra-compact, tunable room temperature Terahertz (THz) emitters with wide-range tunability has stimulated in-depth studies of different mechanisms of THz generation in the past decade due to its various potential applications such as biomedical diagnosis, security screening, chemical identification, life sciences and very high speed wireless communication. Despite the tremendous research and development efforts, all the available state-of-the-art THz emitters suffer from either being large, complex and costly, or operating at low temperatures, lacking tunability, having a very short spectral range and a low output power. Hence, the major objective of this research was to develop simple, inexpensive, compact, room temperature THz sources with wide-range tunability. We investigated THz radiation in a hybrid optical and THz micro-ring resonators system. For the first time, we were able to satisfy the DFG phase matching condition for the above-mentioned THz range in one single device geometry by employing a modal phase matching technique and using two separately designed resonators capable of oscillating at input optical waves and generated THz waves. In chapter 6, we proposed a novel plasmonic antenna geometry – the dimer rod-tapered antenna (DRTA), where we created a hot-spot in the nanogap between the dimer arms with a very large intensity enhancement of 4.1×105 at optical resonant wavelength. Then, we investigated DFG operation in the antenna geometry by incorporating a nonlinear nanodot in the hot-spot of the antenna and achieved continuously tunable enhanced THz radiation across 0.5-10 THz range. In chapter 8, we designed a multi-metallic resonators providing an ultrasharp toroidal response at THz frequency, then fabricated and experimentally demonstrated an efficient polarization dependent plasmonic toroid switch operating at THz frequency. In summary, we have successfully designed, analytically and numerically investigated novel THz emitters with the advantages of wide range tunability, compactness, room temperature operation, fast modulation and the possibility for monolithic integration, which are the most sought after properties in the new generation THz sources.

La prise en compte de machines à traitement par batch dans les problèmes d’ordonnancement d’ateliers complexes de type job-shop est particulièrement difficile. La fabrication de semiconducteurs est probablement l’une des applications pratiques les plus importantes pour ce types de problèmes. Nous considérons un problème d’ordonnancement de type job-shop flexible avec « p-batching », des flux rentrants, des temps de préparation dépendant de la séquence et des dates de début au plus tôt. Le but c’est d’optimiser différentes fonctions objectives régulières.Les approches existantes par graphe disjonctif pour ce problème utilise des nœuds dédiés pour représenter explicitement les batches. Afin de faciliter la modification du graphe conjonctif, notre nouvelle modélisation réduit cette complexité en modélisant les décisions de batching à travers les poids des arcs. Une importante contribution de cette thèse est un algorithme original qui prend les décisions de batching lors du parcours du graphe. Cet algorithme est complété par un déplacement (« move ») intégré qui permet de reséquencer ou réaffecter les opérations. Cette combinaison donne un voisinage riche que nous appliquons dans une approche méta-heuristique de type GRASP.Nous étendons cette approche en prenant en compte de nouvelles contraintes qui ont un rôle important dans l’application industrielle considérée. En particulier, nous modélisons de manière explicite les ressources internes des machines, et nous considérons un temps maximum d’attente entre deux opérations quelconques d’une gamme de fabrication. Les résultats numériques sur des instances de la littérature pour des problèmes plus simples ainsi que sur de nouvelles instances montrent la généricité et l’applicabilité de notre approche. Notre nouvelle modélisation permet de faciliter les extensions à d’autres contraintes complexes rencontrées dans les applications industrielles. / The integration of batching machines within a job-shop environment leads to a complex job-shop scheduling problem. Semiconductor manufacturing presumably represents one of the most prominent practical applications for such problems. We consider a flexible job-shop scheduling problem with p-batching, reentrant flows, sequence dependent setup times and release dates while considering different regular objective functions. The scheduling of parallel batching machines and variants of the job-shop scheduling problem are well-studied problems whereas their combination is rarely considered.Existing disjunctive graph approaches for this combined problem rely on dedicated nodes to explicitly represent batches. To facilitate modifications of the graph, our new modeling reduces this complexity by encoding batching decisions into edge weights. An important contribution is an original algorithm that takes batching decisions “on the fly” during graph traversals. This algorithm is complemented by an integrated move to resequence and reassign operations. This combination yields a rich neighborhood that we apply within a GRASP based metaheuristic approach.We extend this approach by taking further constraints into account that are important in the considered industrial application. In particular, we model internal resources of machines in detail and take maximum time lag constraints into account. Numerical results for benchmark instances of different problem types show the generality and applicability of our approach. The conciseness of our idea facilitates extensions towards further complex constraints needed in real-world applications.

Composites have been developed with great success by the use of fiber reinforcements in metallic materials. Fiber reinforced metal matrices possess great potential to be the next generation of advanced composites offering many advantages compared to fiber reinforced polymers. Specific advantages include high temperature capability, superior environmental stability, better transverse modulus, shear and fatigue properties. Although many Metal Matrix Composites (MMCs) are attractive for use in different industrial applications, Aluminium Matrix Composites (AMCs) are the most used in advanced applications because they combine acceptable strength, low density, durability, machinability, availability, effectiveness and cost. The present study focuses on the fabrication of aluminium matrix composite plates by squeeze casting using plain weave carbon fiber preform (AS4 Hexcel) as reinforcement and a matrix of wrought aluminium alloy 1235-H19. The objective is to investigate the process feasibility and resulting materials properties such as hardness at macro- and micro-scale, impact and bend strength. The properties obtained are compared with those of 6061/1235-H19 aluminium plates that were manufactured under the same fabrication conditions. The effect of fiber volume fraction on the properties is also investigated. Furthermore, the characterization of the microstructure is done using Optical Microscopy (OM) and Scanning Electron Microscopy (SEM) in order to establish relationships between the quality of the fiber/aluminium interface bond and mechanical properties of the composites. In conclusion, aluminium matrix composite laminate plates were successfully produced. The composites show a good chemical bond between the fiber and the aluminium matrix. This bond resulted from heterogeneous precipitation of aluminium carbides (Al4C3) at the interface between aluminium matrix and carbon fiber. The hardness at macro- and micro-scale of the composites increases by over 50% and the flexural modulus increases by about 55%. The toughness of the composite decreases due to the presence of brittle phases which can be improved by better oxidation prevention. Also, an optimal carbon volume fraction was observed that provides optimal properties including peak hardness, peak stiffness and peak toughness.

The 21st century marks the defining point of human history in terms of technological advancement. In 2014, we were at the edge of acquiring a complete understanding of the fundamental construct to all life forms. The capability to manipulate and recreate lives as desired will soon be at our hands and will eventually lead to the redefinition of life and humanity. This brave new world, for better or worse, will be stitched together by scientific breakthroughs in many disciplines. Nanopore fluidic system – and microfluidic in general – might be one of the key puzzles towards the future. It is seen as a likely candidate for the next generation of rapid and low-cost genetic sequencing technology, which will allow us to gain thorough insight into the genetic code of every living organism on earth. It can also have the capability to individually detect and manipulate virtually any biological molecules, possibly allowing it to be a universal diagnostic tool or a bio-molecule synthesiser. The future of nanopore fluidic system is prosperous, but the difficulties are equally challenging. Currently, both biological and solid-state nanopores are non-trivial to create. For instance, a small solid-state nanopore can only be fabricated with expansive machinery in a low-yield, low-throughput manner. To overcome this challenge, a new set of methods involving high electric field to fabricate and enlarge a solid-state nanopore has been developed. It was found that a nanopore, when subjected to a high electric field, can be enlarged in angstrom increments and cleared of unidentified obstructions that cause low-frequency ionic current fluctuations. It was also found that an intact solid-state membrane, when subjected to a high electric field for a period of time, can leave a single nanopore imprinted onto it. The process of creation is best describe as a dielectric breakdown event and can be modeled by the percolation theory for dielectric breakdown. The resulting nanopores are cylindrical in shape and are shown to be equally capable of single molecule sensing compare to pores created by other methods. To accommodate future nanopore designs and applications and to examine the scope of applicability of the new fabrication approach, more advanced nanopore devices were created on some dual-layer solid-state membranes comprising of a metallic and a dielectric layer. Experiments indicated that the method could indeed create nanopore on such advanced membranes. It was further shown that the metallic layer receded further than the dielectric layer, forming a hollow conical shape at the opening of the dielectric nanopore. Such metalized bi-layer nanopore system was found to interact strongly with short single stranded DNA molecules, resulting in prolonged DNA translocation time. A simple picture of the mechanism was proposed to explain the observation. Lastly, to extend the limit of the new fabrication approach, I attempted to fabricate nanopore on complex multi-layer membranes involving a graphene film sandwiched in several dielectric materials. It was found that the quality of the graphene film and the transfer method were vital to the success of this project. Nevertheless, preliminary results indicated that the new method could create a nanopore through this complex multi-layer membrane. The new method to fabricate and tune both simple and complex nanopores is amongst the simplest, the least costly and the most efficient one that one can imagine. The research work has already sparked a dramatic increase in scientific throughput in our laboratory and other laboratories we had collaboration with. It fueled more than a dozen projects and involved close to a thousand nanopores in total. Such projects are far from possible if they were to rely on conventional fabrication methods. However, these are insignificant if we consider the new method is simple enough that, for the very first time, general public can easily access nanofabrication and single-molecule manipulation technology. The liberation of nanotechnology to the general public symbolically marks the beginning of a brave new world.

Initial research in the field of organic electronics focused primarily on the improvements in material performance. Significant progress has been achieved in the case of organic field effect transistors, where reported mobility values are now over 5 orders of magnitude higher than those of early devices. As a consequence, the use of organic transistors is now being considered for real-world applications in the form of integrated logic circuits. This in turn presents many new challenges, as the logic circuit requirements are more demanding on the transistor characteristics and corresponding fabrication processes. This thesis investigates the feasibility of organic technology for its potential use in future low-cost, high-volume electronic applications. The research objectives were accomplished by practical evaluation of an organic logic circuit fabrication process. First, recent advances in the fabrication of organic circuits in terms of transistor structure, material usage and fabrication techniques are reviewed. Next, a lithographic logic circuit fabrication process using PVP gate dielectric and TIPS-pentacene organic semiconductor adapted from state of the art fabrication process is presented. The logic circuit design decisions and the methodology for the fabrication process are thoroughly documented. Using this process, zero-Vgs and diode-load inverter circuits were successfully fabricated. However, the process is in need of further refinement for more complex circuit designs, as the fabrication of a comparator circuit consisting of 11 transistors was unsuccessful. Two optimisation techniques that are compatible with the logic circuit fabrication process were also explored in this work. To improve the capacitive coupling of the dielectric layer, the use of a polymer nanocomposite dielectric was investigated. The nanocomposite is prepared by blending PVP solution with a high-k inorganic nanoparticle filler, barium strontium titanate. Using the nanocomposite dielectric, both single transistors and integrated logic circuits were successfully fabricated. This is the first report on the use of PVP and barium strontium titanate nanocomposite dielectric with a lithographic based logic circuit fabrication process. The use of PFBT modified Au contacts for the fabrication process was investigated to improve theperformance of the contact electrode layer. Using PFBT, mobility increased by one order of magnitude over untreated Au electrodes for the PVP and TIPS-pentacene transistors.

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050 ˚C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1µg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

The way humans currently interact with the atmosphere and oceans around us is unsustainable, with pollution entering our waters faster than we are collecting it, and the sea level rising faster than we are building coastal barriers to protect our current infrastructure. This thesis explores the common methodology for communicating climate change and its future effects, and highlights an opportunity for using infrastructure to facilitate interaction with the urban-aquatic interface. By promoting experiential contact with the natural spaces that are most at risk to climate change’s impacts, a sense of stewardship for those spaces will spur behavioral change and activism. On a local level, this thesis explores the history of public access to San Onofre State Beach, and the possibility for the restriction of that access in 2021. Using a 3D topographic and bathymetric model of San Onofre State Beach, I attempt to highlight the beauty of the undeveloped California coastline, and the benefits of keeping this 6.5-mile coastline within the State Parks system.

Flexible electronics have demonstrated potential in a wide range of applications including wearable sensors, photovoltaics, medical devices and more, due to their properties of extreme adaptability while also being lightweight and highly robust. The main challenge standing in the way of progress in this field is the difficulty of large-scale manufacturing of these flexible electronics compared to their rigid counterparts. Microcontact printing is a form of soft lithography in which an elastomeric stamp is used to transfer sub-micron scale surface patterns onto a flexible substrate via ink monolayers. The integration of microcontact printing into a roll-to-roll (R2R) system will enable continuous printing of flexible electronics and scale it up for massive manufacturing. The proposed thesis outlines a novel mechanical design for a microcontact printer which utilizes flexural motion stages with integrated position and force sensors to control the print process on a R2R system. The printhead is designed to fit the available space on the pre-installed UMass Amherst Intelligent Sensing Laboratory test table and breadboard. The R2R system includes motorized rollers for winding/unwinding the PET (polyethylene terephthalate) web substrate, and idler rollers for guiding a web through the print system. As the central element to this design, two matching plate flexures are designed on the two ends of the printer roller to control the tilting and positioning of the print roller. Flexure mechanisms rely on bending and torsion of flexible elements: this allows them to achieve much higher precision in positioning compared to conventional mechanisms which rely on surface interaction between multiple moving parts. The print resolution target for this design is 500 nm (linewidth), based on current state-of-the-art designs [1, 2]. In the initial version of the printhead design, a total of 33 parts are custom fabricated for assembly and installation in the R2R system lab setup. These include everything from the components of the print roller, specially adapted air-bearing mounts, support structures, and connectors. The design and 4 fabrication process for every component is outlined here along with the functionality, as every component was designed with the system objectives and constraints in mind. Using SolidWorks simulation, FEA (finite element analysis) is performed for every part of the assembly that is subjected to stress in the real system, so that predictions can be made about the displacement of the motion stages and the frequency of vibration. These predictions are evaluated by comparation with the experimental results from tests conducted on the real system hardware and used to assess the quality of the fabricated assembly. The work performed in this thesis enables advancements in the assembly of an updated, optimized R2R system and has led to an experimentally functioning lab setup that is ripe for further improvements. Completion and calibration of this augmented R2R system will, in future, enable UMass Amherst in-house production of large-area flexible electronics which may be used in a wide range of applications, including medical sensors, solar cells, displays, and more. In addition to microcontact printing, this R2R system may also be applied to nanoimprint lithography, another contact-based print method, or integrated with inkjet printing, a non-contact method.

Photovoltaics provide a feasible route to fulfilling the substantial increase in demand for energy worldwide. Solution processable organic photovoltaics (OPVs) have attracted attention in the last decade because of the promise of low-cost manufacturing of sufficiently efficient devices at high throughput on large-area rigid or flexible substrates with potentially low energy and carbon footprints. In OPVs, the photoactive layer is made of a bulk heterojunction (BHJ) layer and is typically composed of a blend of an electron-donating (D) and an electron-accepting (A) materials which phase separate at the nanoscale and form a heterojunction at the D-A interface that plays a crucial role in the generation of charges. Despite the tremendous progress that has been made in increasing the efficiency of organic photovoltaics over the last few years, with power conversion efficiency increasing from 8% to 13% over the duration of this PhD dissertation, there have been numerous debates on the mechanisms of formation of the crucial BHJ layer and few clues about how to successfully transfer these lessons to scalable processes. This stems in large part from a lack of understanding of how BHJ layers form from solution. This lack of understanding makes it challenging to design BHJs and to control their formation in laboratory-based processes, such as spin-coating, let alone their successful transfer to scalable processes required for the manufacturing of organic solar cells. Consequently, the OPV community has in recent years sought out to better understand the key characteristics of state of the art lab-based organic solar cells and made efforts to shed light on how the BHJ forms in laboratory-based processes as well as in scalable processes. We take the view that understanding the formation of the solution-processed bulk heterojunction (BHJ) photoactive layer, where crucial photovoltaic processes take place, is the one of the most crucial steps to developing strategies towards the implementation of organic solar cells with high efficiency and manufacturability. In this dissertation, we investigate the mechanism of the BHJ layer formation during solution processing from common lab-based processes, such as spin-coating, with the aim of understanding the roles of materials, formulations and processing conditions and subsequently using this insight to enable the scalable manufacturing of high efficiency organic solar cells by such methods as wire-bar coating and blade-coating. To do so, we have developed state-of-the-art in situ diagnostics techniques to provide us with insight into the thin film formation process. As a first step, we have developed a modified spin-coater which allows us to perform in situ UV-visible absorption measurements during spin coating and provides key insight into the formation and evolution of polymer aggregates in solution and during the transformation to the solid state. Using this method, we have investigated the formation of organic BHJs made of a blend of poly (3-hexylthiophene) (P3HT) and fullerene, reference materials in the organic solar cell field. We show that process kinetics directly influence the microstructure and morphology of the bulk heterojunction, highlighting the value of in situ measurements. We have investigated the influence of crystallization dynamics of a wide-range of small-molecule donors and their solidification pathways on the processing routes needed for attaining high-performance solar cells. The study revealed the reason behind the need of empirically-adopted processing strategies such as solvent additives or alternatively thermal or solvent vapor annealing for achieving optimal performance. The study has provided a new perspective to materials design linking the need for solvent additives or annealing to the ease of crystallization of small-molecule donors and the presence or absence of transient phases before crystallization. From there, we have extended our investigation to small-molecule (p-DTS (FBTTh2)2) fullerene blend solar cells, where we have revealed new insight into the crucial role of solvent additives. Our work has also touched upon modern polymers, such as PBDTTPD, where we have found the choice of additives impacts the formation mechanism of the BHJ. Finally, we have performed a comparative study of the BHJ film formation dynamics during spin coating versus wire-bar coating of p-DTS(FBTTh2)2: fullerene blends that has helped in curbing the performance gap between lab-based and scalable techniques. This was done by implementing a new apparatus that combines the benefits of rapid thin film drying common to spin coating with scalability of wire-bar coating. Using the new apparatus, we successfully attain similar performance of solar cell devices to the ones fabricated by spin coating with dramatically reduced material waste.