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- All Subjects: Materials Science
- Creators: Krause, Stephen
Description
Transition metal dichalcogenides (TMDs) are a family of layered crystals with the chemical formula MX2 (M = W, Nb, Mo, Ta and X = S, Se, Te). These TMDs exhibit many fascinating optical and electronic properties making them strong candidates for high-end electronics, optoelectronic application, and spintronics. The layered structure of TMDs allows the crystal to be mechanically exfoliated to a monolayer limit, where bulk-scale properties no longer apply and quantum effects arise, including an indirect-to-direct bandgap transition. Controllably tuning the electronic properties of TMDs like WSe2 is therefore a highly attractive prospect achieved by substitutionally doping the metal atoms to enable n- and p-type doping at various concentrations, which can ultimately lead to more effective electronic devices due to increased charge carriers, faster transmission times and possibly new electronic and optical properties to be probed. WSe2 is expected to exhibit the largest spin splitting size and spin-orbit coupling, which leads to exciting potential applications in spintronics over its similar TMD counterparts, which can be controlled through electrical doping. Unfortunately, the well-established doping technique of ion implantation is unable to preserve the crystal quality leading to a major roadblock for the electronics applications of tungsten diselenide. Synthesizing WSe2 via chemical vapor transport (CVT) and flux method have been previously established, but controllable p-type (niobium) doping WSe2 in low concentrations ranges (<1 at %) by CVT methods requires further experimentation and study. This work studies the chemical vapor transport synthesis of doped-TMD W1-xNbxSe2 through characterization techniques of X-ray Diffraction, Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, and X-ray Photoelectron Spectroscopy techniques. In this work, it is observed that excess selenium transport does not enhance the controllability of niobium doping in WSe2, and that tellurium tetrachloride (TeCl4) transport has several barriers in successfully incorporating niobium into WSe2.
ContributorsRuddick, Hayley (Author) / Tongay, Sefaattin (Thesis director) / Jiao, Yang (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2024-05
Description
The vastly growing field of supercomputing is in dire need of a new measurement system to optimize JMRAM (Josephson junction magnetoresistive random access memory) devices. To effectively measure these devices, an ultra-low-noise, low cost cryogenic dipping probe with a dynamic voltage range is required. This dipping probe has been designed by ASU with <100 nVp-p noise, <10 nV offsets, 10 pV to 16 mV voltage range, and negligible thermoelectric drift. There is currently no other research group or company that can currently match both these low noise levels and wide voltage range. Two different dipping probes can be created with these specifications: one for high-use applications and one for low-use applications. The only difference between these probes is the outer shell; the high-use application probe has a shell made of G-10 fiberglass for a higher price, and the low-use application probe has a shell made of AISI 310 steel for a lower price. Both types of probes can be assembled in less than 8 hours for less than $2,500, requiring only soldering expertise. The low cost and short time to create these probes makes wide profit margins possible. The market for these cryogenic dipping probes is currently untapped, as most research groups and companies that use these probes build their own, which allows for rapid business growth. These potential consumers can be easily reached by marketing these probes at superconducting conferences. After several years of selling >50 probes, mass production can easily become possible by hiring several technicians, and still maintaining wide profit margins.
ContributorsHudson, Brooke Ashley (Author) / Adams, James (Thesis director) / Anwar, Shahriar (Committee member) / Materials Science and Engineering Program (Contributor) / W. P. Carey School of Business (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The transition to lead-free solder in the electronics industry has benefited the environment in many ways. However, with new materials systems comes new materials issues. During the processing of copper pads, a protective surface treatment is needed to prevent the copper from oxidizing. Characterizing the copper oxidation underneath the surface treatment is challenging but necessary for product reliability and failure analysis. Currently, FIB-SEM, which is time-consuming and expensive, is what is used to understand and analyze the surface treatment-copper oxide(s)-copper system. This project's goals were to determine a characterization methodology that cuts both characterization time and cost in half for characterizing copper oxidation beneath a surface treatment and to determine which protective surface treatment is the best as defined by multiple criterion such as cost, sustainability, and reliability. Two protective surface treatments, organic solderability preservative (OSP) and chromium zincate, were investigated, and multiple characterization techniques were researched. Six techniques were tested, and three were deemed promising. Through our studies, it was determined that the best surface treatment was organic solderability preservative (OSP) and the ideal characterization methodology would be using FIB-SEM to calibrate a QCM model, along with using SERA to confirm the QCM model results. The methodology we propose would result in a 91% reduction in characterization cost and a 92% reduction in characterization time. Future work includes further calibration of the QCM model using more FIB/SEM data points and eventually creating a model for oxide layer thickness as a function of exposure time and processing temperature using QCM as the primary data source. An additional short essay on the role of SEM on the continuing miniaturization of integrated circuits is included at the end. This paper explores the intertwined histories of the scanning electron microscope and the integrated circuit, highlighting how advances in SEM influence integrated circuit advances.
ContributorsSmith, Bethany Blair (Co-author) / Marion, Branch Kelly (Co-author) / Cruz, Hernandez (Co-author) / Kimberly, McGuiness (Co-author) / Adams, James (Thesis director) / Krause, Stephen (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2015-05

Description
In this work a newly fabricated organic solar cell based on a composite of fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) and regioregular poly (3-hexylthiophene) (P3HT) with an added interfacial layer of AgOx in between the PEDOT:PSS layer and the ITO layer is investigated. Previous equivalent circuit models are discussed and an equivalent circuit model is proposed for the fabricated device. Incorporation of the AgOx interfacial layer shows an increase in fill factor (by 33%) and power conversion efficiency (by 28%). Moreover proper correlation has been achieved between the experimental and simulated I-V plots. The simulation shows that device characteristics can be explained with accuracy by the proposed model.
ContributorsHossain, Nazmul (Author) / Alford, Terry L. (Thesis advisor) / Theodore, David (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2015

Description
The inexorable upsurge in world’s energy demand has steered the search for newer renewable energy sources and photovoltaics seemed to be one of the best alternatives for energy production. Among the various photovoltaic technologies that emerged, organic/polymer photovoltaics based on solution processed bulk-heterojunctions (BHJ) of semiconducting polymers has gained serious attention owing to the use of inexpensive light-weight materials, exhibiting high mechanical flexibility and compatibility with low temperature roll-to-roll manufacturing techniques on flexible substrates. The most widely studied material to date is the blend of regioregular P3HT and PC61BM used as donor and acceptor materials. The object of this study was to investigate and improve the performance/stability of the organic solar cells by use of inexpensive materials. In an attempt to enhance the efficiency of organic solar cells, we have demonstrated the use of hexamethyldisilazane (HMDS) modified indium tin oxide (ITO) electrode in bulk heterojunction solar cell structure The device studies showed a significant enhancement in the short-circuit current as well as in the shunt resistance on use of the hexamethyldisilazane (HMDS) layer. In another approach a p-type CuI hole-transport layer was utilized that could possibly replace the acidic PEDOT:PSS layer in the fabrication of high-efficiency solar cells. The device optimization was done by varying the concentration of CuI in the precursor solution which played an important role in the efficiency of the solar cell devices. Recently a substantial amount of research has been focused on identifying suitable interfacial layers in organic solar cells which has efficient charge transport properties. It was illustrated that a thin layer of silver oxide interfacial layer showed a 28% increase in power conversion efficiency in comparison to that of the control cell. The optoelectronic properties and morphological features of indium-free ZnO/Ag/MoOx electrodes was also studied. Organic solar cells on these composite electrodes revealed good optical and electrical properties, making them a promising alternative indium free and PEDOT:PSS-free organic solar cells. Lastly, inverted solar cells utilizing zinc oxide and yttrium doped zinc oxide electron transport was also created and their device properties revealed that optimum annealing conditions and yttrium doping was essential to obtain high efficiency solar cells.
ContributorsDas, Sayantan (Author) / Alford, Terry L. (Thesis advisor) / Petuskey, William (Thesis advisor) / Buttry, Daniel (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2015

Description
The central theme of this dissertation is to understand the chemical processing science of advanced ceramic materials for biomedicine, including therapy and imaging. The secondary component focuses on the chemical processing of energy materials.
Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging.
Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of fî1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 fÝm thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized.
Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging.
Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of fî1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 fÝm thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized.
ContributorsSun Zhou, Xiao Di (Author) / Dey, Sandwip K (Thesis advisor) / Krause, Stephen (Committee member) / Nagaraj, Vinay J (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014

Description
Transparent conductive oxides (TCO) comprise a class of materials that exhibit unique combination of high transparency in the visible region along with high electrical conductivity. TCOs play an important role as transparent electrodes for optoelectronic devices such as solar cell panels, liquid crystal displays, transparent heat mirrors and organic light emitting devices (OLED). The most commonly used transparent electrodes in optoelectronic applications is indium tin oxide (ITO) due to its low resistivity (~ 10−4 Ω-cm) and high transmittance (~ 80 %). However, the limited supply of indium and the growing demand for ITO make the resulting fabrication costs prohibitive for future industry. Thus, cost factors have promoted the search for inexpensive materials with good electric-optical properties.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
ContributorsDhar, Aritra (Author) / Alford, Terry L. (Thesis advisor) / Petuskey, William (Thesis advisor) / Krause, Stephen (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2015

Description
Rapid processing and reduced end-of-range diffusion effects demonstrate that susceptor-assisted microwave annealing is an efficient processing alternative for electrically activating dopants and removing ion-implantation damage in ion-implanted semiconductors. Sheet resistance and Hall measurements provide evidence of electrical activation. Raman spectroscopy and ion channeling analysis monitor the extent of ion implantation damage and recrystallization. The presence of damage and defects in ion implanted silicon, and the reduction of the defects as a result of annealing, is observed by Rutherford backscattering spectrometry, moreover, the boron implanted silicon is further investigated by cross-section transmission electron microscopy. When annealing B+ implanted silicon, the dissolution of small extended defects and growth of large extended defects result in reduced crystalline quality that hinders the electrical activation process. Compared to B+ implanted silicon, phosphorus implanted samples experience more effective activation and achieve better crystalline quality. Comparison of end-of-range dopants diffusion resulting from microwave annealing and rapid thermal annealing (RTA) is done using secondary ion mass spectroscopy. Results from microwave annealed P+ implanted samples show that almost no diffusion occurs during time periods required for complete dopant activation and silicon recrystallization. The relative contributions to heating of the sample, by a SiC susceptor, and by Si self-heating in the microwave anneal, were also investigated. At first 20s, the main contributor to the sample's temperature rise is Si self-heating by microwave absorption.
ContributorsZhao, Zhao (Author) / Alford, Terry Lynn (Thesis advisor) / Theodore, David (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2013

Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013

Description
This report will review the mechanical and microstructural properties of the refractory element rhenium (Re) deposited using Laser Additive Manufacturing (LAM). With useable structural strength over 2200 °C, existing applications up to 2760 °C, very high strength, ductility and chemical resistance, interest in Re is understandable. This study includes data about tensile properties including tensile data up to 1925 °C, fracture modes, fatigue and microstructure including deformation systems and potential applications of that information. The bulk mechanical test data will be correlated with nanoindentation and crystallographic examination. LAM properties are compared to the existing properties found in the literature for other manufacturing processes. The literature indicates that Re has three significant slip systems but also twins as part of its deformation mechanisms. While it follows the hcp metal characteristics for deformation, it has interesting and valuable extremes such as high work hardening, potentially high strength, excellent wear resistance and superior elevated temperature strength. These characteristics are discussed in detail.
ContributorsAdams, Robbie (Author) / Chawla, Nikhilesh (Thesis advisor) / Adams, James (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2012