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Carbonate-ceramic dual-phase membranes for high temperature carbon dioxide separation

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Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation

Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.

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2011

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Synthesis and stability of ceramic-carbonate dual-phase membrane for carbon dioxide separation

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Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.

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Date Created
2013

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Study of charges present in silicon nitride thin films and their effect on silicon solar cell efficiencies

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As crystalline silicon solar cells continue to get thinner, the recombination of carriers at the surfaces of the cell plays an ever-important role in controlling the cell efficiency. One tool to minimize surface recombination is field effect passivation from the

As crystalline silicon solar cells continue to get thinner, the recombination of carriers at the surfaces of the cell plays an ever-important role in controlling the cell efficiency. One tool to minimize surface recombination is field effect passivation from the charges present in the thin films applied on the cell surfaces. The focus of this work is to understand the properties of charges present in the SiNx films and then to develop a mechanism to manipulate the polarity of charges to either negative or positive based on the end-application. Specific silicon-nitrogen dangling bonds (·Si-N), known as K center defects, are the primary charge trapping defects present in the SiNx films. A custom built corona charging tool was used to externally inject positive or negative charges in the SiNx film. Detailed Capacitance-Voltage (C-V) measurements taken on corona charged SiNx samples confirmed the presence of a net positive or negative charge density, as high as +/- 8 x 1012 cm-2, present in the SiNx film. High-energy (~ 4.9 eV) UV radiation was used to control and neutralize the charges in the SiNx films. Electron-Spin-Resonance (ESR) technique was used to detect and quantify the density of neutral K0 defects that are paramagnetically active. The density of the neutral K0 defects increased after UV treatment and decreased after high temperature annealing and charging treatments. Etch-back C-V measurements on SiNx films showed that the K centers are spread throughout the bulk of the SiNx film and not just near the SiNx-Si interface. It was also shown that the negative injected charges in the SiNx film were stable and present even after 1 year under indoor room-temperature conditions. Lastly, a stack of SiO2/SiNx dielectric layers applicable to standard commercial solar cells was developed using a low temperature (< 400 °C) PECVD process. Excellent surface passivation on FZ and CZ Si substrates for both n- and p-type samples was achieved by manipulating and controlling the charge in SiNx films.

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2013

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Analysis, design, simulation, and measurements of flexible high impedance surfaces

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High Impedance Surfaces (HISs), which have been investigated extensively, have proven to be very efficient ground planes for low profile antenna applications due to their unique reflection phase characteristics. Another emerging research field among the microwave and antenna technologies is

High Impedance Surfaces (HISs), which have been investigated extensively, have proven to be very efficient ground planes for low profile antenna applications due to their unique reflection phase characteristics. Another emerging research field among the microwave and antenna technologies is the design of flexible antennas and microwave circuits to be utilized in conformal applications. The combination of those two research topics gives birth to a third one, namely the design of Conformal or Flexible HISs (FHISs), which is the main subject of this dissertation. The problems associated with the FHISs are twofold: characterization and physical realization. The characterization involves the analysis of scattering properties of FHISs in the presence of plane wave and localized sources. For this purpose, an approximate analytical method is developed to characterize the reflection properties of a cylindrically curved FHIS. The effects of curvature on the reflection phase of the curved FHISs are examined. Furthermore, the effects of different types of currents, specifically the ones inherent to finite sized periodic structures, on the reflection phase characteristics are observed. After the reflection phase characterization of curved HISs, the performance of dipole antennas located in close proximity to a curved HIS are investigated, and the results are compared with the flat case. Different types of resonances that may occur for such a low-profile antenna application are discussed. The effects of curvature on the radiation performance of antennas are examined. Commercially available flexible materials are relatively thin which degrades the bandwidth of HISs. Another practical aspect, which is related to the substrate thickness, is the compactness of the surface. Because of the design limitations of conventional HISs, it is not possible to miniaturize the HIS and increase the bandwidth, simultaneously. To overcome this drawback, a novel HIS is proposed with a periodically perforated ground plane. Copper plated through holes are extremely vulnerable to bending and should be avoided at the bending parts of flexible circuits. Fortunately, if designed properly, the perforations on the ground plane may result in suppression of surface waves. Hence, metallic posts can be eliminated without hindering the surface wave suppression properties of HISs.

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Date Created
2013

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Energy-efficient distributed estimation by utilizing a nonlinear amplifier

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Distributed estimation uses many inexpensive sensors to compose an accurate estimate of a given parameter. It is frequently implemented using wireless sensor networks. There have been several studies on optimizing power allocation in wireless sensor networks used for distributed estimation,

Distributed estimation uses many inexpensive sensors to compose an accurate estimate of a given parameter. It is frequently implemented using wireless sensor networks. There have been several studies on optimizing power allocation in wireless sensor networks used for distributed estimation, the vast majority of which assume linear radio-frequency amplifiers. Linear amplifiers are inherently inefficient, so in this dissertation nonlinear amplifiers are examined to gain efficiency while operating distributed sensor networks. This research presents a method to boost efficiency by operating the amplifiers in the nonlinear region of operation. Operating amplifiers nonlinearly presents new challenges. First, nonlinear amplifier characteristics change across manufacturing process variation, temperature, operating voltage, and aging. Secondly, the equations conventionally used for estimators and performance expectations in linear amplify-and-forward systems fail. To compensate for the first challenge, predistortion is utilized not to linearize amplifiers but rather to force them to fit a common nonlinear limiting amplifier model close to the inherent amplifier performance. This minimizes the power impact and the training requirements for predistortion. Second, new estimators are required that account for transmitter nonlinearity. This research derives analytically and confirms via simulation new estimators and performance expectation equations for use in nonlinear distributed estimation. An additional complication when operating nonlinear amplifiers in a wireless environment is the influence of varied and potentially unknown channel gains. The impact of these varied gains and both measurement and channel noise sources on estimation performance are analyzed in this paper. Techniques for minimizing the estimate variance are developed. It is shown that optimizing transmitter power allocation to minimize estimate variance for the most-compressed parameter measurement is equivalent to the problem for linear sensors. Finally, a method for operating distributed estimation in a multipath environment is presented that is capable of developing robust estimates for a wide range of Rician K-factors. This dissertation demonstrates that implementing distributed estimation using nonlinear sensors can boost system efficiency and is compatible with existing techniques from the literature for boosting efficiency at the system level via sensor power allocation. Nonlinear transmitters work best when channel gains are known and channel noise and receiver noise levels are low.

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Date Created
2013

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Growth and characterization of novel thin films for microelectronic applications

Description

I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin

I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved in the injection of spin polarized electron populations from tunnel junctions containing CFAS electrodes. Epitaxial CFAS thin films with L21 structure and saturation magnetizations of over 1200 emu/cm3 were produced by optimization of the sputtering growth conditions. Point contact Andreev reflection measurements show that the spin polarization at the CFAS electrode surface exceeds 70%. Analyses of the electrical properties of tunnel junctions with a superconducting Pb counter-electrode indicate that transport through native Al oxide barriers is mostly from direct tunneling, while that through the native CFAS oxide barriers is not. ZnGeAs2 is a semiconductor comprised of only inexpensive and earth-abundant elements. The electronic structure and defect properties are similar in many ways to GaAs. Thus, in theory, efficient solar cells could be made with ZnGeAs2 if similar quality material to that of GaAs could be produced. To understand the thermochemistry and determine the rate limiting steps of ZnGeAs2 thin-film synthesis, the (a) thermal decomposition rate and (b) elemental composition and deposition rate of films were measured. It is concluded that the ZnGeAs2 thin film synthesis is a metastable process with an activation energy of 1.08±0.05 eV for the kinetically-limited decomposition rate and an evaporation coefficient of ~10-3. The thermochemical analysis presented here can be used to predict optimal conditions of ZnGeAs2 physical vapor deposition and thermal processing. Pyrite (FeS2) is another semiconductor that has tremendous potential for use in photovoltaic applications if high quality materials could be made. Here, I present the layer-by-layer growth of single-phase pyrite thin-films on heated substrates using sequential evaporation of Fe under high-vacuum followed by sulfidation at S pressures between 1 mTorr and 1 Torr. High-resolution transmission electron microscopy reveals high-quality, defect-free pyrite grains were produces by this method. It is demonstrated that epitaxial pyrite layer was produced on natural pyrite substrates with this method.

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Date Created
2013

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Energy and quality-aware multimedia signal processing

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Today's mobile devices have to support computation-intensive multimedia applications with a limited energy budget. In this dissertation, we present architecture level and algorithm-level techniques that reduce energy consumption of these devices with minimal impact on system quality. First, we present

Today's mobile devices have to support computation-intensive multimedia applications with a limited energy budget. In this dissertation, we present architecture level and algorithm-level techniques that reduce energy consumption of these devices with minimal impact on system quality. First, we present novel techniques to mitigate the effects of SRAM memory failures in JPEG2000 implementations operating in scaled voltages. We investigate error control coding schemes and propose an unequal error protection scheme tailored for JPEG2000 that reduces overhead without affecting the performance. Furthermore, we propose algorithm-specific techniques for error compensation that exploit the fact that in JPEG2000 the discrete wavelet transform outputs have larger values for low frequency subband coefficients and smaller values for high frequency subband coefficients. Next, we present use of voltage overscaling to reduce the data-path power consumption of JPEG codecs. We propose an algorithm-specific technique which exploits the characteristics of the quantized coefficients after zig-zag scan to mitigate errors introduced by aggressive voltage scaling. Third, we investigate the effect of reducing dynamic range for datapath energy reduction. We analyze the effect of truncation error and propose a scheme that estimates the mean value of the truncation error during the pre-computation stage and compensates for this error. Such a scheme is very effective for reducing the noise power in applications that are dominated by additions and multiplications such as FIR filter and transform computation. We also present a novel sum of absolute difference (SAD) scheme that is based on most significant bit truncation. The proposed scheme exploits the fact that most of the absolute difference (AD) calculations result in small values, and most of the large AD values do not contribute to the SAD values of the blocks that are selected. Such a scheme is highly effective in reducing the energy consumption of motion estimation and intra-prediction kernels in video codecs. Finally, we present several hybrid energy-saving techniques based on combination of voltage scaling, computation reduction and dynamic range reduction that further reduce the energy consumption while keeping the performance degradation very low. For instance, a combination of computation reduction and dynamic range reduction for Discrete Cosine Transform shows on average, 33% to 46% reduction in energy consumption while incurring only 0.5dB to 1.5dB loss in PSNR.

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2012

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Energy efficient RF transmitter design using enhanced breakdown voltage SOI-CMOS compatible MESFETs

Description

The high cut-off frequency of deep sub-micron CMOS technologies has enabled the integration of radio frequency (RF) transceivers with digital circuits. However, the challenging point is the integration of RF power amplifiers, mainly due to the low breakdown voltage of

The high cut-off frequency of deep sub-micron CMOS technologies has enabled the integration of radio frequency (RF) transceivers with digital circuits. However, the challenging point is the integration of RF power amplifiers, mainly due to the low breakdown voltage of CMOS transistors. Silicon-on-insulator (SOI) metal semiconductor field effect transistors (MESFETs) have been introduced to remedy the limited headroom concern in CMOS technologies. The MESFETs presented in this thesis have been fabricated on different SOI-CMOS processes without making any change to the standard fabrication steps and offer 2-30 times higher breakdown voltage than the MOSFETs on the same process. This thesis explains the design steps of high efficiency and wideband RF transmitters using the proposed SOI-CMOS compatible MESFETs. This task involves DC and RF characterization of MESFET devices, along with providing a compact Spice model for simulation purposes. This thesis presents the design of several SOI-MESFET RF power amplifiers operating at 433, 900 and 1800 MHz with ~40% bandwidth. Measurement results show a peak power added efficiency (PAE) of 55% and a peak output power of 22.5 dBm. The RF-PAs were designed to operate in Class-AB mode to minimize the linearity degradation. Class-AB power amplifiers lead to poor power added efficiency, especially when fed with signals with high peak to average power ratio (PAPR) such as wideband code division multiple access (W-CDMA). Polar transmitters have been introduced to improve the efficiency of RF-PAs at backed-off powers. A MESFET based envelope tracking (ET) polar transmitter was designed and measured. A low drop-out voltage regulator (LDO) was used as the supply modulator of this polar transmitter. MESFETs are depletion mode devices; therefore, they can be configured in a source follower configuration to have better stability and higher bandwidth that MOSFET based LDOs. Measurement results show 350 MHz bandwidth while driving a 10 pF capacitive load. A novel polar transmitter is introduced in this thesis to alleviate some of the limitations associated with polar transmitters. The proposed architecture uses the backgate terminal of a partially depleted transistor on SOI process, which relaxes the bandwidth and efficiency requirements of the envelope amplifier in a polar transmitter. The measurement results of the proposed transmitter demonstrate more than three times PAE improvement at 6-dB backed-off output power, compared to the traditional RF transmitters.

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2012

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Efficient test strategies for Analog/RF circuits

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Test cost has become a significant portion of device cost and a bottleneck in high volume manufacturing. Increasing integration density and shrinking feature sizes increased test time/cost and reduce observability. Test engineers have to put a tremendous effort in order

Test cost has become a significant portion of device cost and a bottleneck in high volume manufacturing. Increasing integration density and shrinking feature sizes increased test time/cost and reduce observability. Test engineers have to put a tremendous effort in order to maintain test cost within an acceptable budget. Unfortunately, there is not a single straightforward solution to the problem. Products that are tested have several application domains and distinct customer profiles. Some products are required to operate for long periods of time while others are required to be low cost and optimized for low cost. Multitude of constraints and goals make it impossible to find a single solution that work for all cases. Hence, test development/optimization is typically design/circuit dependent and even process specific. Therefore, test optimization cannot be performed using a single test approach, but necessitates a diversity of approaches. This works aims at addressing test cost minimization and test quality improvement at various levels. In the first chapter of the work, we investigate pre-silicon strategies, such as design for test and pre-silicon statistical simulation optimization. In the second chapter, we investigate efficient post-silicon test strategies, such as adaptive test, adaptive multi-site test, outlier analysis, and process shift detection/tracking.

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Date Created
2012

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Improving the reliability of NAND Flash, phase-change RAM and spin-torque transfer RAM

Description

Non-volatile memories (NVM) are widely used in modern electronic devices due to their non-volatility, low static power consumption and high storage density. While Flash memories are the dominant NVM technology, resistive memories such as phase change access memory (PRAM) and

Non-volatile memories (NVM) are widely used in modern electronic devices due to their non-volatility, low static power consumption and high storage density. While Flash memories are the dominant NVM technology, resistive memories such as phase change access memory (PRAM) and spin torque transfer random access memory (STT-MRAM) are gaining ground. All these technologies suffer from reliability degradation due to process variations, structural limits and material property shift. To address the reliability concerns of these NVM technologies, multi-level low cost solutions are proposed for each of them. My approach consists of first building a comprehensive error model. Next the error characteristics are exploited to develop low cost multi-level strategies to compensate for the errors. For instance, for NAND Flash memory, I first characterize errors due to threshold voltage variations as a function of the number of program/erase cycles. Next a flexible product code is designed to migrate to a stronger ECC scheme as program/erase cycles increases. An adaptive data refresh scheme is also proposed to improve memory reliability with low energy cost for applications with different data update frequencies. For PRAM, soft errors and hard errors models are built based on shifts in the resistance distributions. Next I developed a multi-level error control approach involving bit interleaving and subblock flipping at the architecture level, threshold resistance tuning at the circuit level and programming current profile tuning at the device level. This approach helped reduce the error rate significantly so that it was now sufficient to use a low cost ECC scheme to satisfy the memory reliability constraint. I also studied the reliability of a PRAM+DRAM hybrid memory system and analyzed the tradeoffs between memory performance, programming energy and lifetime. For STT-MRAM, I first developed an error model based on process variations. I developed a multi-level approach to reduce the error rates that consisted of increasing the W/L ratio of the access transistor, increasing the voltage difference across the memory cell and adjusting the current profile during write operation. This approach enabled use of a low cost BCH based ECC scheme to achieve very low block failure rates.

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2014