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- All Subjects: Materials Science
- Creators: Krause, Stephen
- Creators: Adams, James
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
III-Nitride nanostructures have been an active area of research recently due to their ability to tune their optoelectronic properties. Thus far work has been done on InGaN quantum dots, nanowires, nanopillars, amongst other structures, but this research reports the creation of a new type of InGaN nanostructure, nanorings. Hexagonal InGaN nanorings were formed using Metal Organic Chemical Vapor Deposition through droplet epitaxy. The nanorings were thoroughly analyzed using x-ray diffraction, photoluminescence, electron microscopy, electron diffraction, and atomic force microscopy. Nanorings with high indium incorporation were achieved with indium content up to 50% that was then controlled using the growth time, temperature, In/Ga ratio and III/N ratio. The analysis showed that the nanoring shape is able to incorporate more indium than other nanostructures, due to the relaxing mechanism involved in the formation of the nanoring. The ideal conditions were determined to be growth of 30 second droplets with a growth time of 1 minute 30 seconds at 770 C to achieve the most well developed rings with the highest indium concentration.
ContributorsZaidi, Zohair (Author) / Mahajan, Subhash (Thesis advisor) / O'Connell, Michael J (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2012
Description
Zinc oxide (ZnO) has attracted much interest during last decades as a functional material. Furthermore, ZnO is a potential material for transparent conducting oxide material competing with indium tin oxide (ITO), graphene, and carbon nanotube film. It has been known as a conductive material when doped with elements such as indium, gallium and aluminum. The solubility of those dopant elements in ZnO is still debatable; but, it is necessary to find alternative conducting materials when their form is film or nanostructure for display devices. This is a consequence of the ever increasing price of indium. In addition, a new generation solar cell (nanostructured or hybrid photovoltaics) requires compatible materials which are capable of free standing on substrates without seed or buffer layers and have the ability introduce electrons or holes pathway without blocking towards electrodes. The nanostructures for solar cells using inorganic materials such as silicon (Si), titanium oxide (TiO2), and ZnO have been an interesting topic for research in solar cell community in order to overcome the limitation of efficiency for organic solar cells. This dissertation is a study of the rational solution-based synthesis of 1-dimentional ZnO nanomaterial and its solar cell applications. These results have implications in cost effective and uniform nanomanufacturing for the next generation solar cells application by controlling growth condition and by doping transition metal element in solution.
ContributorsChoi, Hyung Woo (Author) / Alford, Terry L. (Thesis advisor) / Krause, Stephen (Committee member) / Theodore, N. David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Ball Grid Array (BGA) using lead-free or lead-rich solder materials are widely used as Second Level Interconnects (SLI) in mounting packaged components to the printed circuit board (PCB). The reliability of these solder joints is of significant importance to the performance of microelectronics components and systems. Product design/form-factor, solder material, manufacturing process, use condition, as well as, the inherent variabilities present in the system, greatly influence product reliability. Accurate reliability analysis requires an integrated approach to concurrently account for all these factors and their synergistic effects. Such an integrated and robust methodology can be used in design and development of new and advanced microelectronics systems and can provide significant improvement in cycle-time, cost, and reliability. IMPRPK approach is based on a probabilistic methodology, focusing on three major tasks of (1) Characterization of BGA solder joints to identify failure mechanisms and obtain statistical data, (2) Finite Element analysis (FEM) to predict system response needed for life prediction, and (3) development of a probabilistic methodology to predict the reliability, as well as, the sensitivity of the system to various parameters and the variabilities. These tasks and the predictive capabilities of IMPRPK in microelectronic reliability analysis are discussed.
ContributorsFallah-Adl, Ali (Author) / Tasooji, Amaneh (Thesis advisor) / Krause, Stephen (Committee member) / Alford, Terry (Committee member) / Jiang, Hanqing (Committee member) / Mahajan, Ravi (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
Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, ∆EDA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt-16. Furthermore, the development of a series of tetradentate Pt complexes yielded highly efficient and stable single doped white devices due to their halogen free tetradentate design. In addition to these benchmark achievements, the systematic molecular modification of both emissive and absorbing materials provides valuable structure-property relationship information that should help guide further developments in the field.
ContributorsFleetham, Tyler Blain (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2014
Description
Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases.
In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated.
Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a microcavity organic light emitting diode (MOLED), significant enhancement in the external quantum efficiency was achieved. The optimized MOLED structure achieved a light out-coupling enhancement of 1.35 compared to the non-cavity structure with a peak EQE of 34.2%. In addition to demonstrating a high light out-coupling enhancement, the microcavity effect of a narrow band emitter in a MOLED was elucidated.
In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated.
Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a microcavity organic light emitting diode (MOLED), significant enhancement in the external quantum efficiency was achieved. The optimized MOLED structure achieved a light out-coupling enhancement of 1.35 compared to the non-cavity structure with a peak EQE of 34.2%. In addition to demonstrating a high light out-coupling enhancement, the microcavity effect of a narrow band emitter in a MOLED was elucidated.
ContributorsEcton, Jeremy David (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
Description
Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl components in the ligand. These complexes possess interesting luminescent properties including ultra-narrow emission and metal assisted delayed fluorescence (MADF) emission.
ContributorsTurner, Eric (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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