In the electroplating process, dissolved metal cations are reduced by electrical current to a form a coherent metal coating on an electrode. Therefore, electroplating is primarily applied to modify the surface properties of an object (e.g. abrasion and wear resistance, corrosion protection, lubricity, aesthetic qualities, etc.), but also be applied to build up high aspect ratio structures on undersized parts or to form devices by electroforming. Compared with other common MEMS (microelectromechanical systems) metal device fabrication techniques, such as vapor depositions, electroplating has several outstanding advantages. First, the fabrication process is cost-efficient because electroplating process can be set up easily without complex and expensive facilities. Second, the fabrication condition of electroplating is less demanding and does not require high temperature or low pressure. Furthermore, the process is applicable to making various features consisting of nanometer to millimeter scale particles, wires, and films. Thus, in this thesis, based on the design requirements of electrospray emitters and environmental sensors, the electroplating method was chosen to fabricate micro- and nanoscale structures for such applications. Electrospray is an atomization technique by which an electrically conductive liquid through a small capillary is charged with high voltage (kV) and ejected to a ground electrode. To minimize the electric field edge effect of the emitter nozzles to get even electro-hydrodynamic pulling force on the liquid among the nozzles and minimize variation from one emitter to another, the device needs to have the viscous pressure drop across each nozzle dominant over the electro-hydrodynamic pulling force. Therefore, embedded structures that can create high flow impedance are desirable to achieve uniform feeding of low flow rate of liquid to each emitter. We designed and fabricated in-plane metallic electrospray devices with an embedded array of micropillars within a microchannel by photolithography and electroplating. The novelty of the proposed research lies in its embedded flow restriction structure, scalability, and ease of fabrication. The formation of jets as well as the flexing capability of the emitter was achieved. The other application of electroplating was demonstrated in the fabrication of environmental sensors. Utilizing a pulsed electroplating method, Co-Cu metal alloy films were prepared and Cu was selectively etched to fabricate nanoporous electrodes which could be used to measure both absolute levels and changes of phosphate concentration in aqueous environments. The formation of cobalt phosphate compound could be used for the detection. The increased surface area and relatively simple fabrication protocols make the proposed method attractive and promising for many environmental sensing applications.

Phosphorus is needed by living organism including humans and plants, to survive. Imbalance in phosphate concentration in human body can result in numerous diseases or disorders while excess phosphorus levels in water bodies like lakes, and rivers, are responsible for the rise in incidence of algal bloom across world. Current commercial phosphate monitoring systems are dominated by colorimetric measurements while electrochemical sensors including potentiometric, amperometric and voltammetric sensors are still in the research phase. Electrochemical sensors require stable reference electrodes for reliable measurements that pose challenges for miniaturization. Solid state potentiometric sensors are widely explored due to their rapid response, easy fabrication and simple electronic measurement system. However, the sensor miniaturization is dependent both on the working and reference electrode. Metal electrodes like cobalt offers advantages such as reagent-free detection, easy to miniaturize but the sensitivity of zero-current potentiometric sensors is limited by the theoretical Nernstian limit and cobalt sensors also require chemical pretreatment in standard solution before measurement. Here, an in situ electrical pretreatment method is proposed to eliminate the need of chemical pretreatment and enhance the sensitivity of cobalt electrodes to -91.4 mV/ decade of phosphate concentration. However, this electrode still needs a reference electrode for reliable measurements. Therefore, this study has demonstrated a chemiresistive sensing platform for solid state detection of phosphate using both enzyme and enzyme-free methods. A rapid prototyping method was developed to pattern the thin metal films (~100 nm thickness) using a bench top plotter cutter. The method was used to fabricate thin gold film contact electrodes for chemiresistors. The thin gold leaf contact electrodes exhibited low-noise and offered a robust, rapid and reproducible manufacturing process for chemiresistors. The chemiresistive sensor showed a wide measuring range (0.5 ppm to 500 ppm) for hydrogen peroxide detection. The sensor was deposited with glucose oxidase to demonstrate the application of the sensor for peroxidase assays to detect glucose in standard buffer solution and human pooled plasma. Phosphate also is detected using pyruvate oxidase in presence of pyruvate to generate hydrogen peroxide as the detectable molecule. Finally, metal phthalocyanines were used to perform enzyme-free phosphate measurements. This work demonstrated the sensor technologies which could be used for in-field phosphate monitoring to prevent algal bloom and it also provides phosphate monitoring methods for rapid detection in medical diagnostics for early diagnosis for diseases like chronic kidney disease and to improve the patient’s outcomes for such diseases. / Thesis / Doctor of Philosophy (PhD) / Phosphorus is an essential element for the survival of living beings including humans and plants because it is needed in multiple physiological pathways and functions like cellular signalling, energy storage, metabolism and maintenance. Therefore, phosphate in the human body is strictly regulated and in disease conditions like chronic kidney disease, and metabolic disorders. It can increase or decrease resulting in ailments and worsening of diseases. Phosphorus is also extensively used in the agricultural field to improve the growth and crop yield. Excess phosphorus from these fertilizers can enter our water sources via agricultural water run-offs leading to the increasing incidences of algal bloom across world. Current phosphorus measuring systems require chemicals which generates toxic waste, needs manual sample collection and transport, and have narrow measuring ranges. There is an urgent need for sensors which would eliminate the need of sample collection and processing, do not require toxic chemicals and could work over a wide detection range. This study presents two solid-state sensor technologies which would simplify the phosphate detection for both environmental and medical diagnostics samples.

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