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Lead (Pb) levels in tap water below the established water safety guideline are now considered harmful, thus detecting sub-parts-per-billion level Pb is important. This thesis reports on a miniaturized Copper (Cu)−based electrochemical sensor fabricated from thick film electrodes for their superior sensing performance. These thick film electrodes are based on highly conductive rolled-annealed Cu foil that has a compact bulk structure, but these advantages are often offset by the fact that RA Cu foil is difficult to bond to a substrate due to poor film-adhesion property and lack of mechanical interlocks. For this reason, we develop a direct bonding process for Cu/polymer. An integrated three-electrode planar configuration is then fabricated on the bonded specimen to achieve a fully-functional sensor that can detect 0.2 μg/L (0.2 ppb) Pb2+ ions from a 100 μL sample in only 30 s. This is the most rapid detection of Pb featured to date by an all Cu-based sensor. This thesis first focuses on improving substrate adhesion of RA Cu foil to liquid crystal polymer (LCP). This is achieved by a surface activated bonding process where Cu and LCP surfaces are treated with low-power reactive ion etching oxygen plasma followed by low-pressure contact at 230 °C. This treatment produces hydroxyl (OH−) groups on Cu and LCP surfaces making them highly hydrophilic. When Cu and LCP are contacted and heated, the OH− chains condense by dehydration and form an intermediate oxide layer. This layer mainly develops as Cu2O nanoparticles from the plasma-treated Cu side due to thermal oxidation in air. These nanoparticles diffuse into the polymer substrate when heated under mechanical pressure, resulting in a strongly bonded flexible specimen for the sensor. A simple, inexpensive, and production-friendly fabrication process is then developed for these sensors. Following direct bonding, flexible Cu/LCP is fed into a LaserJet printer for a one-step transfer of polyester resin−based electrode mask on Cu. This is followed by etching, packaging, and a chlorinating process to achieve a fully-functional integrated sensor. The sensing performance of directly bonded Cu/LCP is comparable to that of commercially available Cu/polyimide (PI) laminate. Our approach holds promise towards realizing low-cost integrated water quality monitoring systems. Thesis Master of Applied Science (MASc) Lead contamination in tap water has major health risks for which monitoring of its levels is important. In this thesis, we develop a low-cost copper/polymer-based lead sensor. The sensor is fabricated from high-quality metal foil electrodes that are integrated to a polymer substrate by a direct bonding process. This enables strong adhesion of foil-based electrodes to the substrate that is crucial to the sensor performance and packaging integrity. We investigate the bonding mechanism between copper and polymer to understand the fundamentals of materials integration. These findings will lead to the development of polymer-based sensors and integrated systems. The bonded sensor bases are mechanically flexible, which facilitates a rapid and low-cost fabrication process using a laser printer. The developed sensor has a fast response time (30 s) and can detect very low levels of lead, thus making it suitable for water quality monitoring applications in under-developed and developed countries with legacy water systems that have not been upgraded yet.

The monitoring of pH and free chlorine concentration in drinking water is important for water safety and public health. However, existing laboratory-based analytical methods are laborious, inefficient, and costly. This thesis focuses on the development of an easy-to-use, sensitive, and low-cost drinking water quality monitoring system for pH and free chlorine. An inkjet printing technology with a two-step thermolysis process in air is developed to deposit palladium/palladium oxide (Pd/PdO) films as potentiometric pH sensing electrodes. The redox reaction between PdO and hydronium ions generates the sensor output voltage. A large PdO percentage in the film provides a high sensitivity of ~60 mV/pH. A defect-free Pd/PdO film with small roughness contributes to a fast response and a high stability. When the Pd ink is thermalized in low vacuum, the deposited Pd/PdO film shows a bilayer structure. The residual oxygen in the low vacuum environment assists the decomposition of organic ligands for Pd to form a thin and continuous layer beneath submicron Pd aggregates. The oxidized bilayer film behaves as a temperature sensor with a sensitivity of 0.19% resistance change per °C, which can be used to compensate the sensed pH signals. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is drawn by hand to form a free chlorine sensor. Free chlorine oxidises PEDOT:PSS, whose resistivity increment indicates the free chlorine concentration in the range of 0.5-500 ppm. Also, we simplified an amperometric free chlorine sensor based on amine-modified pencil leads. The simplified sensor is calibration-free, potentiostat-free, and easy-to-use. The pH, temperature, and free chlorine sensors are fabricated on a common substrate and connected to a field-programmable gate array board for data processing and display. The sensing system is user-friendly, cheap, and can accurately monitor real water samples. Thesis Doctor of Philosophy (PhD) Sensitive, easy-to-use, and low-cost pH and free chlorine monitoring systems are important for drinking water safety and public health. In this thesis, we develop an inkjet printing technology to deposit palladium/palladium oxide films for potentiometric pH sensors and resistive temperature sensors. The different electrical and electrochemical properties of the palladium/palladium oxide films are realized by creating different film morphologies using different ink thermolysis atmospheres. The developed pH and temperature sensors are highly sensitive, fast in response, and stable. For free chlorine sensors, a hand drawing process is used to deposit poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), which is an indicator for the free chlorine concentration over a wide range. We also developed a calibration-free free chlorine sensors based on modified pencil leads. Such a free chlorine sensor is integrated with the pH and temperature sensors, and an electronic readout system for accurate on-site drinking water quality monitoring at low cost is demonstrated.

We propose a physically based model that describes the density and size of voids in silicon introduced via high dose helium ion implantation and subsequent annealing. The model takes into account interactions between vacancies, interstitials, small vacancy clusters, and voids. Void evolution in silicon occurs mainly by a migration and coalescence process. Various factors such as implantation energy and dose, anneal temperature, atmospheric pressure, and impurity level in silicon can influence the migration and coalescence mechanism and thus play a role in the void evolution process. Values for model parameters are consistent with known values for point defect parameters and assumed diffusion limited reaction rates. A single “fitting parameter” represents the rate of bubble migration and coalescence and is therefore related to surface diffusion of adatoms. Results obtained from simulations based upon the model were compared to our experimental results and to previously reported experimental results obtained over a wide range of conditions. Our own experiments involved the implantation of silicon samples and samples with a thin Si1-xGex (x = 0.05, 0.09) epilayer on silicon with 30 keV, 5×1016 cm-2 helium. Anneals were done in the range 960-1110°C for 15-30 minutes in nitrogen and dry oxygen. Void size distributions were measured from transmission electron microscopy images. Average void diameter and void density values and void size distribution did not show any significant differences between the samples annealed in nitrogen and dry oxygen. However, the presence of Si1-xGex epilayer on silicon resulted in increased average void diameter and reduced average void density when compared with Si samples as well as more selective void size distribution. Data from the literature included experiments with helium ion implantation energies in the range 30 - 300 keV, doses of 1×1016 - 1×1017 cm-2, subsequent annealing temperatures in the range 700 - 1200°C, and annealing duration in the range 15 minutes - 2 hours. Excellent agreement is found between the simulated results and those from reported experiments. The extracted migration and coalescence rate parameter shows an activation energy consistent with surface diffusivity of silicon. It shows a linear dependence on helium dose, and increases with decreased implantation energy, decreased ambient pressure, decreased substrate impurities, increased temperature ramp rate, or increased Ge fraction in cavity layer, all consistent with the proposed physical mechanism. Our mathematical model specifically ignores the long time saturation in void size, although we propose a simple explanation consistent with the physical picture. Similarly, we give physical reasons for a threshold implant dose resulting in the formation of small vacancy clusters during implant. But in modeling void growth we simply show that when such clusters exist voids will evolve according to our model. In our experiments, the presence of a Si0.95Ge0.05 epilayer on silicon resulted in retarded B diffusion when compared with Si samples. This phenomenon is correlated to the role of the Si0.95Ge0.05 epilayer on silicon in the void evolution mechanism and both are attributed to Ge interdiffusing from the epilayer into the Si bulk. The B diffusion data also allows us to predict conditions for the SiGe epilayer to modify the injection of interstitials from surface during dry oxidizing anneal. Doctor of Philosophy (PhD)