Yttria stabilized Zirconia (8YSZ) is an extensively used solid electrolyte, which finds applications in electrochemical sensors, solid oxide fuel cells and gate oxide in MOSFETs. Recent studies report that YSZ thin films are better performers than their bulk counterparts, in terms of ionic conductivity even at moderate temperatures. YSZ thin films also attract attention with the scope of device miniaturization. However, most of the studies available in the literature on YSZ thin films focus mainly on their electrical characterization. In this work, YSZ thin films were deposited, characterized and possible use of sensors were evaluated. In the present work, 8 mol% yttria stabilized zirconia thin films were deposited using RF magnetron reactive sputtering under different deposition conditions. Films with thicknesses ranging from few tens to few hundreds of nanometres were deposited. The deposited films were subjected to morphological, structural, compositional and electrical characterizations. Deposition and annealing conditions were optimized to obtain dense, stoichiometric and crystalline YSZ thin films. The ionic conductivity of 200 nm nanocrystal line thin film was found to be two orders of magnitude higher than the bulk. The ionic conductivity increased with the decrease in film thickness. Compositional analyses of a set of YSZ thin films revealed free surface yttrium segregation. The free surface segregation of dopants can locally alter the surface chemistry and influence the oxygen transfer kinetics across the electrode-electrolyte interface. Although number of reports are available on the segregation characteristics in YSZ bulk, no reports are available on yttria segregation in YSZ thin film. Hence, this work reports detailed investigations on the free surface yttria segregation in YSZ thin films using angle resolved X-ray photoelectron spectroscopy (XPS). Influence of annealing temperature, film thickness, annealing time, and purity on the segregation concentration was determined. It was found that the most important factor that determines the segregation was found to be the target purity. The segregation depth profile analysis showed that the segregation layer depth was proportional to segregation concentration. Free surface segregation reduced the ionic conductivity of the YSZ thin films roughly about a factor. However, segregation did not affect the film’s morphology, grain size, crystallinity and activation energy. The difference in ionic conductivity observed in the segregated and clean YSZ films suggests that dopant free surface segregation could also be one of the reasons for the variable ionic conductivity reported in the literature. For using YSZ in miniaturized devices, micro-structuring of YSZ is important. It has been reported that the wet etching techniques available for YSZ were not repeatable and do not etch annealed YSZ samples. Reactive ion etching (RIE) is better suited for YSZ patterning due to its capability to offer high resolution, easy control and tenable anisotropic/isotropic pattern transfer for batch processing. Although reports are available on the dry etching of zirconia and yttria thin films, no studies were reported on the dry etching of YSZ thin films. In this work, inductively coupled reactive ion etching (ICP-RIE) using fluorine and chlorine chemistries were employed to etch YSZ thin films. Optimized etching conditions were identified by varying different process parameters like, type of gas, gas flow rate, RF power, ICP power, chamber pressure and carrier wafer in the ICP-RIE process. Optimized conditions were chosen by examining the etch depth, composition analyses before and after etch using XPS, selectivity towards SiO2 (which is the most common buffer layer) and surface roughness. Etch chemistries involved in a particular plasma (SF6, Cl2 and BCl3) were discussed with the help of surface composition and etch thicknesses. The results showed that etching YSZ with BCl3 plasma at optimized conditions yielded best results through oxygen-scavenging mechanism. A maximum etch rate of 53 nm/min was obtained in BCl3 plasma using PECVD Si3N4 carrier wafer at an ICP power of 1500 W, RF power of 100 W, chamber pressure of 5 mTorr with 30 sccm BCl3 flow. Sensing devices were designed by employing YSZ thin film as solid electrolyte and nickel oxide and gold thin film as sensing and reference electrodes, respectively to evaluate the possible use of YSZ thin film in miniaturized NO2 sensor. The electrodes were deposited in inter-digitated pattern. Two types of electrodes were designed with different number of fingers in symmetric and asymmetric configurations. The NO2 sensing was performed in the concentration range of 25 to 2000 ppm at three different temperatures, 673, 773 and 873 K in mixed potential and impedance metric modes. The mixed potential type measurements were carried out only for asymmetric cell in two different electrode configurations. The impedance metric type measurements were carried out for both symmetric and asymmetric cells in two different electrode configurations. Preliminary NO2 sensing experiments in both the types of measurements revealed that in devices with electrodes having more fingers were better in performance. In mixed potential type sensors, sensitivity was measured as the amount of voltage generated when the sensor was exposed to a test gas. The generated voltage was found to be proportional to the logarithm of NO2 concentration in the entire measurement range (50 to 2000 ppm) with the regression fitting parameter, adj.R2 around 0.97 to 0.99 in all the cases. A maximum potential of 271 mV was measured with 2000 ppm NO2 at 873 K. The response and recovery times of the sensors were sensitive to the operating temperature. In impedance metric mode, the sensitivities were measured as the variation in the low frequency phase angle (∆ φ) when the gas concentration is changed. The frequency range of the measurement was from 0.01 Hz to100 kHz. The response time in the impedance metric sensors was comparable to that of mixed potential sensors. But the recovery time in impedance metric sensors was much was slower than the mixed potential type for all the concentrations. The sensors showed linear response only in a narrow range of 50 to 500 ppm with regression fitting value, R2 around 0.98 in all the cases. Above 500 ppm, the sensitivity value was observed to be saturated. From the gas sensing studies performed on the miniaturized sensors, it was found that the mixed potential type sensing mode is better than the impedance metric type in YSZ thin film based devices. However detailed interference gas studies were needed before drawing any conclusion. In summary, the studies presented in the work have contributed to the understanding of free surface yttria segregation behaviour in YSZ thin films. Micromachining conditions were optimized for both pristine and annealed YSZ thin films. Suitability of YSZ thin film based miniaturized NO2 gas sensor was evaluated.

With the discovery of conductivity in doped polyacetylene (PA), a new era in synthetic metals has emerged by breaking the traditionally accepted view that polymers were always insulating. Conducting polymers are essentially characterized by the presence of conjugated bonding on the polymeric back bone, which facilitates the formation of polarons and bipolarons as charge carriers. Among the numerous conducting polymers synthesized to date, polypyrrole (PPy) is by far the most extensively studied because of prodigious number of applications owing to its facile polymerizability, environmental stability, high electrical conductivity, biocompatibility, and redox state dependent physico-chemical properties. Electrochemically prepared PPy is more interesting than the chemically prepared polymer because it adheres to the electrode surface and can be directly used for applications such as supercapacitors, electrochemical sensors, electromechanical actuators and drug delivery systems. In quest for improvement in quality of the device performances in the mentioned applications, micro and nano structured polymeric materials which bring in large surface area are studied. Finding a simple and efficient method of synthesis is very important for producing devices of PPy microstructures. Till date, Hard and soft template methods are the most employed methods for synthesis of these structures. Soft template based electrochemical methods are better than hard template methods to grow clean PPy microstructures on electrode substrates as procedures for removal of hard templates after the growth of microstructures are very complex. As per the literature, there is no unique method available to grow PPy microstructures which can demonstrate several applications. Although gas bubble based soft template methods are exploited to grow conducting polymer microstructures of sizes in few hundreds of micrometers, studies on applications of the same are limited. Hence it is planned to develop procedures to grow microstructures that can be used in several applications. In the current work, PPy microstructures with high coverage densities are synthesized on various electrode substrates by soft template based electrochemical techniques. Hollow, hemispherical and spherical PPy microstructures are developed by a two step method using electro generated hydrogen bubble templates on SS 304 electrodes. In the first step, Hydrogen bubbles are electro generated and stabilized on the electrode in the presence of β- naphthalene sulfonic acid (β-NSA). In the second step, Pyrrole is oxidised over the bubble template to form PPy microstructures. Microstructures (open and closed cups) of average size 15 μm are uniformly spread on the surface with a coverage density of 2.5×105 units /cm2. Globular PPy microstructures are developed by a single step method using concomitantly electro generated oxygen bubble templates on SS 304 electrodes during electropolymerization. Microstructures of average size 4 μm are uniformly spread on the surface with a coverage density of 7×105 units/cm2. Surfactant properties of Zwitterionic 4-(2-hydroxyethyl)-1-piperazine ethane sulfonic acid (HEPES) are exploited for the first time to grow conducting polymer microstructures. Ramekin shaped PPy microstructures are developed using HEPES as the surfactant to stabilize hydrogen bubble templates in a two step electrochemical synthesis method. Microramekins of size 100 µm are uniformly spread on the surface with a coverage density of 3000 units/cm2. Micropipettes and microhorns of PPy are synthesised by a single step electrochemical route using HEPES as a surfactant. Hollow micropipettes of length 7 µm with an opening of 200 nm at the top of the structure are observed. Similarly microhorn/celia structures are observed with length 10-15 µm. Microcelia are uniformly distributed over the surface with each structure having a diameter of 2 µm at the base to 150 nm at the tip. Growth mechanism based on contact angle of the reactant solution droplets on the substrate is proposed. PPy microstructures are characterized by scanning electron microscopy, X-Ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman Spectroscopy and UV-Visible spectroscopy to study morphology, ‘chemical bonding and structure’ , ‘defects and charge carriers’. Applicability of the electrodes with PPy microstructures in supercapacitors is investigated by cyclic voltammetry, chronopotentiometry and electrical impedance spectroscopy. Electrodes developed by all the above methods demonstrated very good supercapacitance properties. Supercapacitor studies revealed very high specific capacitances (580, 915, 728 and 922 F/g,) and specific powers (20, 25, 13.89 and 15.91 kW/kg) for electrodes with PPy microstructures (H2 bubble based two step method, O2 bubble based single step method, HEPES stabilized H2 bubbble method and HEPES based microhorn/celia structures respectively). Supercapacitive behavior of all the electrodes is retained even after an extended charge-discharge cycling in excess of 1500 cycles. Horseradish peroxidase entrapped, bowl shaped PPy microstructures are developed for H2O2 biosensing. Amperometric biosensor has a performance comparable to the sensors reported in the literature with high sensitivity value of 12.8 μA/(cm2.mM) in the range 1.0 mM to 10 mM. Glucose oxidase entrapped PPy amperometric biosensor is developed for Glucose sensing. Sensitivity of 1.29 mA/(cm2.mM) is observed for β-D-Glucose sensing in the 0.1 mM to 5.0 mM range while 58 μA/(cm2.mM) is observed in the 5.0 to 40 mM range. Potentiometric urea sensor with urease entrapped PPy microstructures on SS electrode is developed. It is able to sense urea in the micromolar ranges down to 0.1 μM. It represented an excellent performance with sensitivity of 27 mV/decade. Sensitivity in the micromolar range is 4.9 mV/(μM.cm2). Drug encapsulation and delivery is successfully demonstrated by two actuation means (i) by electrochemical actuation, (ii) by actuation based on pH changes. Concepts are proved by delivering a fluorescent dye into neutral and acidic solutions. Drug delivery is confirmed by UV-Visible spectroscopy and Fluorescence microscopy. Finally, Micro/nanostructures with Tangerine, Hollow globular (Pani Poori), Chip, Flake, Rose, Worm, Horn and Celia shapes are synthesized electrochemically and scanning electron microscopic studies are presented. Controlled growth of microstructures on lithographically patterned gold interdigital electrodes is demonstrated with a future goal of creating addressable microstructures. The studies reported in the thesis provide an insight on various applications of PPy microstructures (supercapacitors, sensors and drug delivery systems) developed by a unique methodology based on electrochemically generated gas bubble templates.

This PhD research relates to the design, fabrication, characterization, and optimization of on-chip electrochemical microelectrode arrays (MEAs) for measurement of transient concentrations and gradients, focusing on fast transients and physiological applications. In particular, this work presents the determination of kinetic mechanisms taking place at an active interface (either physiological or non-physiological) in contact with a liquid phase using the MEA device to simultaneously estimate the concentration and gradient of the analyte of interest at the surface of the active interface. The design approach of the MEA device and the corresponding measurement methodology to acquire reliable concentration information is discussed. The ability of the MEA device to measure fast (i.e., in sub-second time scale) transient gradients is demonstrated experimentally using a controllable diffusion-reaction system which mimics the consumption of hydrogen peroxide by a 2D cell culture. The proposed MEA device and measurement methodology meet effectively most of the requirements for physiological applications and as a demonstration of this, two physiological applications are presented. In one application, the MEA device was tailored to measure the hydrogen peroxide uptake rate of human astrocytes and glioblastoma multiforme cells in 2D cell culture as a function of hydrogen peroxide concentration at the cell surface; the results allowed to quantitatively determine the uptake kinetics mechanisms which are well-described by linear and Michaelis-Menten expressions, in agreement with the literature. In the other application, further customization of the MEA device was realized to study the glucose uptake kinetics of human bronchial epithelial and small cell lung cancer cells, these latter with and without DDX5 gene knockdown; the results allowed to distinguish mechanistic differences in the glucose uptake kinetics among the three cell lines. These results were complemented with measurements of glycolytic and respiration rates to obtain a bigger picture of the glucose metabolism of the three cell lines. Finally, additional applications, both physiological and non-physiological, are proposed for the developed MEA device.

In 2D cell cultures uptake/release of various metabolic analytes such as glucose, lactate or metabolic by-products like hydrogen peroxide from/to the extracellular environment results in concentration gradients. The magnitude, direction, and time scales of these gradients carries information that is essential for internal cellular processes and/or for communication with neighboring cells. This PhD research work focusses on the design, fabrication and characterization of electrochemical microelectrode arrays (MEAs) optimized to be positioned in commonly used 2D cell culture setups. Importantly, by simultaneously measuring accurate concentration transients and associated gradients/uxes near the cell surface (surface concentration) the capability of the device to quantify kinetic rates and distinguish mechanisms involved in various cellular processes is demonstrated. An in-situ transient calibration technique suitable for amperometric MEAs is developed and the technique is validated by quantitatively measuring dynamic concentration profiles with varying spatial (100-800 µm) and time (s to hrs.) scales set up from an electrically controlled diffusion reaction system. With the proposed MEA design and technique three physiological applications are demonstrated. Firstly, the position able 1D MEA was employed real time to quantitatively measure the hydrogen peroxide scavenging rates from astrocyte vs glioblastoma cell cultures. With the ability to extract to dynamic surface concentration and fluxes, the cell lines were shown to have hydrogen peroxide uptake rates dependent on local surface concentrations. Moreover, the cancerous glioblastoma cells demonstrated an upregulated linear peroxide scavenging mechanism as compared to astrocytes. For the next phase, spatial scales of 1D MEA device along the size and functionalization scheme of the electrodes in the MEA was further modified to selectively sense glucose and lactate to enable extracellular metabolic profiling of cancer vs normal cell lines. Secondly, measurement of glucose concentration profiles demonstrated an increased glucose uptake rate in glioblastoma as compared to astrocytes. Additionally, sigmoidal (allosteric) vs Michaelis - Menten glucose uptake kinetics was observed in glioblastoma vs astrocytes. Moreover, the presence of a glucose sensing mechanism was observed in glioblastoma cells due to the dependence of the glucose uptake rate on initial exposed concentration rather than surface concentration. Finally, simultaneous multi-analyte (glucose and lactate) gradient measurements were performed on genetically modified mouse pancreatic cancer cell lines. While glucose uptake rate was shown to increase with increasing extracellular glucose concentration for one of the cell lines, the lactate release rate was observed to be independent of the initial extracellular glucose dose.

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / The presence of organic and inorganic pollutants in aqueous environments is one of the major challenges confronting man. It is therefore important to develop sensitive, versatile and cheap techniques for their detection. Arsenic (III), 2-chlorophenol (2-CP) and sulfamethoxazole (SMX) are priority pollutants that pose health threats to humans and animals. This study was thus aimed at exploring two promising carbon nanomaterials as electrode modifiers for the electrochemical sensing of arsenic (III), 2-CP and SMX in water. Glassy carbon electrode (GCE) was modified with a nanocomposite of carbon dots (CDs) and graphitic carbon nitride (g-C3N4) and used as a sensor for the analytes in aqueous media. The CDs was prepared by a facile one-pot hydrothermal method using pine cone as the carbon source; g-C3N4 and g-C3N4/CDs nanocomposite were prepared via the microwave irradiation heating method. CDs, g-C3N4 and g-C3N4/CDs were dropped-dried on the surface of bare GCE. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the prepared materials. GCE, g-C3N4/GCE, CDs/GCE and g-C3N4/CDs/GCE electrodes were electrochemically investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) using a ferrocyanide [Fe (CN) 6]3-/4- redox probe. The current and the reversibility of the redox probes were enhanced in the presence of modifiers. The electrochemical behavior of arsenic (III), 2-CP and SMX on different electrodes (GCE, CDs/GCE, g-C3N4/GCE and g-C3N4/CDs/GCE) were investigated by differential pulse voltammetry (DPV) under optimized conditions in a phosphate buffer solution (pH 7.6, 6 and 5 for 2-CP, As (III) and SMX respectively). The results demonstrated that the g-C3N4/CDs/GCE electrode significantly enhanced the oxidation peak current of all three analytes. The detection sensitivity of the analytes was greatly improved, suggesting that this new modified electrode has great potential in the determination of trace level of arsenic (III), 2-CP and SMX in water. The oxidation peak currents displayed a linear relationship to concentrations for 2-CP (0.5 - 2.5 μM, R2=0.958, n=5), arsenic (III) (2 - 10 μM R2=0.978, n=5) and SMX (0.3 - 1.3 μM R2=0.9906, n=5). The detection limits of 0.62 μM, 1.64 μM and 0.10 μM were obtained for 2-CP, arsenic and SMX, respectively. Phenol and 4-chloro-3-methyl-phenol were found to interfere with the detection of 2-CP, while, Cu2+, Zn2+, Pb2+ and Cd2+ were the only significant ions that interfered with the electrochemical detection of arsenic (III). EDTA was used as a ligand to mask the interference effects of copper, cadmium, lead and zinc on arsenic sensing. The modified electrode (g-C3N4/CDs/GCE) was used to determine arsenic, 2-CP and SMX in spiked tap and effluent water samples by the standard addition method and the results showed percentage recoveries varying from 93-118% for 2-CP, 98-100% for arsenic and 80-105% for SMX. The outcomes of this study established that the nanocomposite material represents an easy and sensitive sensing platform for the monitoring of arsenic (III), 2-CP and SMX in aqueous media.

The monitoring of pharmaceuticals, heavy metal, pH and free chlorine concentration in drinking water is important for public health and the environment. However, conventional laboratory-based analytical methods are labor-intensive, expensive, and time consuming. This thesis focuses on developing an integrated, highly sensitive, easy-to-use, and low-cost pharmaceuticals, heavy metal, pH and free chlorine sensing system for drinking water quality monitoring. A low-temperature, solution-processed modification of multi-walled carbon nanotubes (MWCNT) with β-cyclodextrin (βCD) on glassy carbon electrode is developed for detecting low levels of acetaminophen. The adsorption properties of βCD are combined with the high surface area of carbon nanotubes towards enhanced electrochemical sensing of acetaminophen with a limit of detection of 11 nM and linear range from 0.05-300 μM. Also, a systematic investigation is carried out using four types of modified MWCNT-βCD. A novel, one-step approach called Steglich esterification modified MWCNT-βCD results in large effective surface area, and fast electron transfer towards sensitive detection of acetaminophen and 17β-estradiol (E2, primary female sex hormone) in the range of 0.005–20 and 0.01–15 μM, with low detection limits of 3.3 and 2.5 nM, respectively. The similar MWCNT-βCD modified electrodes can also detect heavy metal ion (lead, Pb2+) with a limit of detection of <10 ppb. Low frequency noise behavior of these sensors are studied. A spin-coated Pd/PdO based pH sensor, and amine-modified carbon electrode-based free chlorine sensor are fabricated on a common substrate together with the pharmaceuticals and heavy metal sensors. A Wheatstone-bridge temperature sensor is fabricated based on silicon and PEDOT:PSS on another substrate. All the sensors are connected to an Arduino microcontroller based data acquisition system with a smartphone application interface. The integrated sensing system is easy-to-use, low-cost, and can provide accurate monitoring data with real drinking water samples. / Dissertation / Doctor of Philosophy (PhD) / Low-cost, easy-to-use, and sensitive monitoring system for pharmaceuticals, heavy metal, pH and free chlorine in drinking water is crucial for public health safety. In this thesis, we develop solution-based synthesis of multi-walled carbon nanotubes modified by β-cyclodextrin for electrochemical sensing of pharmaceuticals and heavy metal. The modification approaches are compared and characterized to analyze their electrochemical behavior and sensing performances. The developed sensors are highly sensitive toward the detection of acetaminophen (a widely used pain-killer) and estrogen hormone in drinking water. We also develop a modified spin-coating technique to deposit palladium/palladium oxide films for potentiometric pH sensor, a calibration-free free chlorine sensor based on modified carbon electrode, and a resistive temperature sensor. The developed pH, free chlorine and temperature sensors are highly sensitive, and stable with fast response time. All the sensors are integrated and interfaced with a custom-made and smartphone-controlled electronic readout system for accurate and on-site drinking water quality monitoring at low cost.

Magister Scientiae - MSc (Chemistry) / Pollutants such as polycyclic aromatic hydrocarbons (PAHs) are known for their toxic effects which may lead to the cause of degenerative diseases in both humans and animals. PAHs are widespread in the environment, and may be found in water, food, automotive industry and petrochemical industries to name but a few sources. Literature reports have highlighted industrial workplace exposure to PAHs as a leading cause for development of cancer in workers. Particularly, workers in the petrochemical industry are adversely affected and the incidence of skin and lung cancer in this population group is high. The United States of America in its guidelines developed by environmental protection agency (EPA) has identified 18 PAHs as priority pollutants. Among these are anthracene, benzo[a]pyrene and pyrene which have been selected as the focal point of this study due to their significance in the petrochemical industry. Due to the carcinogenic and mutagenic properties reported in literature for certain PAHs, there have been monitoring procedures taken in most countries around the world. The commonly used analytical methods for the detection of PAHs from industrial samples are high performance liquid chromatography (HPLC) coupled to fluorescence detection, membrane filtration, ozonation and reverse osmosis. Analysis of PAHs from the petrochemical industry is typically performed by HPLC method as well as sono-degredation in the presence of oxygen and hydrogen peroxide.

<p>The development of low-cost, and reliable platforms for on-site detection of pathogenic agents, and toxic environmental traces is still a critical need for real-time monitoring of potential environmental pollution and imminent outbreaks. The biosensors market is projected to attain 31.5 billion by 2024. In this landscape, colorimetric and electrochemical devices continue to have significant relevance, with paper-based platforms leading the point-of-care (POC) segment for pathogen detection and environmental monitoring.</p> <p>Despite the true potential of biosensors in general, they have witnessed a slow rate in commercialization, mainly due to cost restrictions, and concerns related to their reliability and repeatability once scaled-up. This research evaluates the implementation of printing techniques as a strong approach for the fabrication of paper-based and flexible electrochemical biosensors. The results obtained demonstrated the ability to control and predict the variables affecting the sensing performance, achieving high precision of the printing parameters, and allowing optimization, and iterations since very early stages of prototype development.</p> <p>Besides the novel fabrication approach, this work introduces the use of truncated aptameric DNA sequences for whole cell detection of E. coli O157:H7 and heavy metals (Hg2+ and As3+), providing evidence of high stability and robustness under harsh conditions. Results obtained demonstrate their equal or even superior performance when compared to antibodies.</p> <p>We established the use of aptamer-functionalized multilayered label particles (PEI-grafted gold decorated polystyrene) with high stability as label particles. These particles address the well known drawback of non-selective aggregation typical of traditional naked Gold nanoparticles. The outstanding stability of these multilayered labels was demonstrated when used in an enhanced version of the lateral flow assay for detection of E. coli O157:H7 (state of the art for paper-based colorimetric detection of whole cell bacteria), and in a multiplexed paper-based microfluidic device for dual detection of Mercury and Arsenic. This work sets the foundation of the development of a next generation of health care and environmental monitoring devices that are portable, sensitive, quantitative, and can reliably detect multiple targets with one single test.</p>