In this thesis, we design electrode shape of light emitter diode (LED) to help the current diffusing uniformly. The purpose of the uniform current is to avoid the waste heat from the devices and enhance the efficiency of active region. The LED samples adopted in this study are GaN base materials grown on sapphire. The P-N electrodes must be processed on the same side since the poor conductivity of sapphire. The same side P-N electrode will results in current crowding phenomena. We design special electrode shapes to make the current diffuse uniformly and reduce the current crowding phenomena. First, we use COMSOL simulation software to simulate the current spreading between the electrodes. We adopt the same parameters from the reference papers to confirm the reliabilities of the simulation. Then we simulate several electrode shapes with highly uniform current spreading. Second, we use the simulation results to fabricate electrode on chips. The first set is LED without transparent conductive layer. This set is to confirm whether the fabrication processes is feasible and adjust the simulation parameters at the same time. The second set is LED with transparent conductive layer. The experimental emission intensity has deviation from the simulation results. We deduce the emission intensities from smaller LED chip size will have great influence on illumination surface. The third set is electrodes fabricated on large size LED chip. The electrode patterns successfully enhance the uniformity of current spreading, and enhance the output light intensity of 21%. The current density distribution trend from simulation is matched with the illumination intensities.

In this study, the carbon electrode of supercapacitor was fabricated by using mesocarbon microbeads. For finding the optimal processing parameters of carbon electrode, the effects of specific surface area of activated carbon, the amount of carbon black and binder, and various electrolytes on the capacitative properties of supercapacitor are investigated. To fabricate the composite electrode of supercapacitor, NiO and WO3 thin films were deposited respectively on the carbon electrode by electron beam evaporation. The influences of various scan rates of cyclic voltammograms (CV) on the characteristic of capacitance are studied. The charge-discharge efficiency and life time of the composite electrode are also discussed. Experimental results reveal that the optimum carbon electrode can be obtained using mesocarbon microbeads with high specific surface area (2685 m2/g) and larger pore volume (0.6 cm3/g) and adding 10 wt.% carbon black and 2wt.% binder. The specific capacitances of carbon electrodes in 1 M KOH and 1 M Et4NBF4 are 230.8 F/g and 221.5 F/g, respectively. Besides, the XRD and SEM results showed that NiO and WO3 thin films on composite electrode are sheet-liked crystal structure and stone-liked amorphous structure, respectively. The composite electrode exhibits better capacitance properties than those of carbon electrode at high scan rate by CV analysis. It reveals the promotion of the capacitative property of supercapacitor at higher power density and the improving of the decay property in capacitance at high scan rate. Finally, in the test of charge-discharge efficiency and life time, the charge-discharge efficiency is near 100% after 5000 cycles and it still retains good adhesion between electrode material and substrate.

The fabrication and characterization of boron-doped diamond microelectrodes for use in electrochemical detection coupled with capillary electrophoresis (CE-EC) is discussed. They exhibited low and stable background currents and sigmoidally shaped voltammetric curves for cysteine, cystine and Fe(CN)63-/4- . Evaluation of the CE-EC system and the electrode performance were accomplished using a 10 mM borate buffer, pH 8.8, run buffer, and a 70-cm-long fused-silica capillary (10-mm i.d.) with seven sulfur-containing amino acids (methionine, cysteine, cystine, homocysyeine, homocystine, glutathionine, glutathionine disulfide) as test analytes. Reproducible separation (elution time) and detection (peak current) of seven sulfur-containing amino acids were observed with response precisions of 5% or less.

The microstructure and electrochemical behavior of boron doped and undoped ultra thin diamond film electrodes have been studied in this work. The ultra thin diamond films are deposited on porous silicon (PSi) by microwave plasma chemical vapor deposition (MPCVD). In order to enlarge the surface area of diamond electrodes, the deposition of nano structured diamond thin films is performed only in a short time deposition under a negative bias, so that diamond nuclei grew from the tips of PSi nano structures and the thin film surface remained rough and nano fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM, and then fabricated to the electrode device. From SEM analysis, the morphology of diamond thin films on PSi reveals in the shape of nano rods diamond crystallites. The electro-chemical response was evaluated by performing cyclic voltammetry in the inorganic K4[Fe(CN)6] and a K2HPO4 buffer solution. Boron doped diamond thin film on porous silicon has demonstrated a high redoxidation current of cyclic voltammetry, which may be due to the rough surface providing more electrochemical surface area and more sp2 conducting bonds exposed on the surface.

none

Capping is typically used to control contaminant release from the underlying sediments. However, the presence of conventional caps often eliminates or slows natural degradation that might otherwise occur at the surface sediment. This is primarily due to the development of reducing conditions within the sediment that discourage hydrocarbon degradation. The objective of this study was to develop a novel active capping method, an electrode enhanced cap, to manipulate the redox potential to produce conditions more favorable for hydrocarbon degradation and evaluate the approach for the remediation of PAH contaminated sediment. A preliminary study of electrode enhanced biodegradation of PAH in sediment slurries showed that naphthalene and phenanthrene concentration decreased significantly within 4 days, and PAH degrading genes increased by almost 2 orders of magnitude. In a sediment microcosm more representative of expected field conditions, graphite cloth was used to form an anode at the sediment-cap interface and a similar cathode was placed a few centimeters above within a thin sand layer. With the application of 2V voltage, ORP increased and pH dropped around the anode reflecting water electrolysis. Various cap amendments (buffers) were employed to moderate pH changes. Bicarbonate was found to be the most effective in laboratory experiments but a slower dissolving buffer, e.g. siderite, may be more effective under field conditions. Phenanthrene concentration was found to decrease slowly with time in the vicinity of the anode. In the sediment at 0-1 cm below the anode, phenanthrene concentrations decreased to ~70% of initial concentration with no bicarbonate, and to ~50% with bicarbonate over ~70 days, whereas those in the control remained relatively constant. PAH degrading gene increased compared with control, providing microbial evidence of PAH biodegradation. A voltage-current relationship, which incorporated separation distance and the area of the electrodes, was established to predict current. A coupled reactive transport model was developed to simulate pH profiles and model results showed that pH is neutralized at the anode with upflowing groundwater seepage. This study demonstrated that electrode enhanced capping can be used to control redox potential in a sediment cap, provide microbial electron acceptors, and stimulate PAH degradation. / text

This dissertation explores cathodic electrodeposition mechanisms that describe the synthesis of redox-active electrode materials. Several interesting elements are known to deposit at negative potentials (e.g., Mo, Re, Se), and by extending this work, we can tailor the growth of new binary systems (e.g., MoxRe₁₋xOy, MoxSe₁₋xOy) that have enhanced optical and electronic properties. To grasp the subtleties of deposition and understand how the growth of a particular phase is influenced by other species in solution, several analytical methodologies are used to thoroughly characterize film deposition, including chronocoulometry, voltammetry, nanogravimetry, UV-Visible spectroelectrochemistry, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and inductively coupled plasma mass spectrometry (ICPMS). Chapter 1 is a general introduction that discusses the growth of redox-active metal oxides and alloys with an emphasis on tuning the composition to enhance material performance. Chapter 2 proposes a mechanistic pathway for the deposition of rhenium films from an acidic perrhenate (ReVIIO₄⁻) solution containing both metallic and oxide components. Unlike many other metal anions, it was observed that ReVIIO₄⁻ adsorbs to the electrode surface prior to reduction. As such, ReVIIO₄⁻ is ideally situated to be a redox-active mediator for other electrochemical reactions, and in Chapter 3, this dissertation explores how ReVIIO₄⁻ increases the deposition efficiency of Mo oxide deposition. Depth profiling XPS supported by electrochemical studies demonstrated that Mo and Re deposit separately to form an inhomogeneous material, MoxRe₁₋xOy (0.6 < x ≤ 1.0). Over a limited potential range from –0.3 V to –0.7 V (vs Ag/AgCl) the rhenium mole fraction increases linearly with the applied voltage. Chapter 4 explores the deposition of MoxSe₁₋xOy, and in this case, the incorporation of Mo species in solution shifts the deposition of Se⁰ to more positive potentials. Depending on the applied potential used, voltammetry experiments suggest that a small amount of Mo (<5%) reduces to the zero-valent phase to yield the photosensitive alloy, MoxSey. Chapter 5 discusses future work and presents preliminary data describing the deposition of Se⁰ on ITO using adsorbed ReVIIO₄⁻ as a redox mediator. / text

Neural electrodes are an important part of brain-machine interface devices that can restore functionality to patients with sensory and movement impairments including spinal cord injury and limb loss. Currently, chronically implanted neural electrodes induce an unfavorable tissue response which includes inflammation, scar formation, and neuronal cell death, eventually causing loss of electrode functionality in the long term. The objective of this research was to develop a coating to improve the tissue response to implanted neural electrodes. The hypothesis was that coating the surface of neural electrodes with a non-fouling, anti-inflammatory coating would cause reduced inflammation and a better tissue response to the implanted electrode. We developed a polymer coating with non-fouling characteristics, incorporated an anti-inflammatory agent, and engineered a stimulus-responsive degradable portion for on-demand release of the anti-inflammatory agent in response to inflammatory stimuli. We characterized the coating using XPS and ellipsometry, and analyzed cell adhesion, cell spreading, and cytokine release in vitro. We analyzed the in vivo tissue response using immunohistochemistry and microarray qRT-PCR. Although no differences were observed among the samples for inflammatory cell markers, lower IgG penetration into the tissue around PEG + IL-1Ra coated electrodes suggests an improvement in BBB integrity. Gene expression analysis showed higher expression of IL-6 and MMP-2 around PEG + IL-1Ra samples, as well as an increase in CNTF expression, an important marker for neuronal survival. An important finding from this research is the increased neuronal survival around coated electrodes compared to uncoated controls, which is a significant finding as neuronal survival near the implant interface is an essential part of maintaining electrode functionality.

The development of wireless DNA microelectrochemical microarray sensors is described. The operational principles of these sensors are based on bipolar electrochemistry. Bipolar electrodes are used to fabricate the wireless microarrays in this work. The systems are configured so that DNA sensing is carried out at the cathodic end of a bipolar electrode (BPE) and the result of the sensing experiment is reported at the anodic end of the BPE. There are two types of reporting platforms developed in this study. The first type relies on the emission of electrogenerated chemiluminescence (ECL). The system is configured so that ECL is emitted at the anodic end of the BPE when the target DNA is hybridized to the capture probe DNA immobilized on the cathodic end of the BPE. However, when there is no hybridization reaction occurs, there is no ECL emission on the electrode surface. The second type of reporting platform developed is based on silver electrodissolution at the anodic end of a BPE. When a reduction reaction occurs at the cathodic end of a BPE, it triggers oxidation and dissolution of silver deposited at the anodic end of the BPE. The loss of silver can easily be detected by the naked eye. This detection principle is used for DNA detection: when the target DNA is hybridized to capture probe DNA on the BPE, the BPE becomes shorter. However, if target DNA does not hybridize to the electrode surface, the length of the BPE remains the same. The BPE microarrays described in this work eliminate the need for complicated microfabrication procedures and instrumentation. For example, as many as 1000 BPEs can be simultaneously controlled using just two driving electrodes and a simple power supply. To fully utilize BPE microarrays for specific sensing tasks, a method based on robotic spotting was developed to modify the cathodic end of each BPE in the array. Because each BPE in a microarray is individually addressable, this development allows each BPE to perform a particular sensing operation. / text

Organic photovoltaics (OPVs) offer the prospect of inexpensive processing compared with conventional crystalline semiconductor cells. These cells are still lower in efficiency than their inorganic counterparts, in part because a detailed understanding of the role that interfaces play in these devices is lacking. The electronic properties of the surface of the common transparent electrode Indium:Tin Oxide (ITO) have been studied both on a macroscopic and nanoscopic scale, and the interface between ITO and organic materials has been studied on a macroscopic scale as well. Little work has been done on the nanoscopic properties of the ITO/organic interface. This dissertation introduces a new conducting-probe atomic force microscope (CP-AFM) technique, Scanning Current Spectroscopy (SCS), for probing the nanoscopic lateral variation in the electronic properties of this interface, and demonstrates its utility by examining the ITO/copperphthalocyanine (CuPc) interface. SCS demonstrates large lateral variations in the hole collection efficiency at that interface on a nanometer length scale, and that the distribution of these variations is affected by ITO pretreatment. Measurements on OPVs demonstrate that the performance of these devices is dependant on the nanoscopic lateral variation in surface properties that SCS measures, and that in the case of the ITO/CuPcinterface SCS explains the observed device behavior better than techniques that yield macroscopic average electronic properties, such as photoelectron spectroscopy. Additionally, this dissertation discusses advances made in the design of an integrated optical refractive index sensor. The sensor uses organic light-emitting diodes (OLEDs) and OPVs as integrated light-sources and detectors on top of a slab waveguide substrate. The platform offers potentially high sensitivities to refractive index changes (and the selective binding of chemical and biological analytes), and is amenable to largescale integration for on-chip multiplexed detection. The refractive index response has been demonstrated previously, but the performance was limited by electrical noise and OLED drift. The use of different absorbing species in the OPV, integration of multiplesensors on a single substrate, addition of a reference channel to monitor OLED drift andthe use of lock-in amplification for signal processing allow the sensor to detect changesof 10-4 refractive index units.