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In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO2-La2O3/ZnO/SiO2/Si, and c) HfO2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO2/SiO2 are determined to be 3.4 ± 0.1, 1.5 ± 0.1, and 0.7 ± 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen plasma may induce excess oxygen species with negative charges, which could be removed by He plasma treatment. The final HfO2 capping layer deposition may reduce the internal potential inside the structures. The band structure was approaching to a flat band condition.
ContributorsZhu, Chiyu (Author) / Nemanich, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Chen, Tingyong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Engineered pavements cover a large fraction of cities and offer significant potential for urban heat island mitigation. Though rapidly increasing research efforts have been devoted to the study of pavement materials, thermal interactions between buildings and the ambient environment are mostly neglected. In this study, numerical models featuring a realistic representation of building-environment thermal interactions, were applied to quantify the effect of pavements on the urban thermal environment at multiple scales. It was found that performance of pavements inside the canyon was largely determined by the canyon geometry. In a high-density residential area, modifying pavements had insignificant effect on the wall temperature and building energy consumption. At a regional scale, various pavement types were also found to have a limited cooling effect on land surface temperature and 2-m air temperature for metropolitan Phoenix. In the context of global climate change, the effect of pavement was evaluated in terms of the equivalent CO2 emission. Equivalent CO2 emission offset by reflective pavements in urban canyons was only about 13.9e46.6% of that without building canopies, depending on the canyon geometry. This study revealed the importance of building-environment thermal interactions in determining thermal conditions inside the urban canopy.
ContributorsYang, Jiachuan (Author) / Wang, Zhi-Hua (Author) / Kaloush, Kamil (Author) / Dylla, Heather (Author)
Created2016-08-22
Description
Water affinity and condensation on Si-based surfaces is investigated to address the problem of fogging on silicone intraocular lenses (IOL) during cataract surgery, using Si(100), silica (SiO2) and polydimethylsiloxane (PDMS) silicone (SiOC2H6)n. Condensation is described by two step nucleation and growth where roughness controls heterogeneous nucleation of droplets followed by Ostwald ripening. Wetting on hydrophilic surfaces consists of continuous aqueous films while hydrophobic surfaces exhibit fogging with discrete droplets. Si-based surfaces with wavelength above 200 nm exhibit fogging during condensation. Below 200 nm, surfaces are found to wet during condensation. Water affinity of Si-based surfaces is quantified via the surface free energy (SFE) using Sessile drop contact angle analysis, the Young-Dupré equation, and Van Oss theory. Topography is analyzed using tapping mode atomic force microscopy (TMAFM). Polymer adsorption and ion beam modification of materials (IBMM) can modify surface topography, composition, and SFE, and alter water affinity of the Si-based surfaces we studied. Wet adsorption of hydroxypropyl methylcellulose (HPMC) C32H60O19 with areal densities ranging from 1018 atom/cm2 to 1019 atom/cm2 characterized via Rutherford backscattering spectrometry (RBS), allows for the substrate to adopt the topography of the HPMC film and its hydrophilic properties. The HPMC surface composition maintains a bulk stoichiometric ratio as confirmed by 4.265 MeV 12C(α, α)12C and 3.045 MeV 16O(α, α)16O, and 2.8 MeV He++ elastic recoil detection (ERD) of hydrogen. Both PIXE and RBS methods give comparable areal density results of polymer films on Si(100), silica, and PDMS silicone substrates. The SFE and topography of PDMS silicone polymers used for IOLs can also be modified by IBMM. IBMM of HPMC cellulose occurs during IBA as well. Damage curves and ERD are shown to characterize surface desorption accurately during IBMM so that ion beam damage can be accounted for during analysis of polymer areal density and composition. IBMM of Si(100)-SiO2 ordered interfaces also induces changes of SFE, as ions disorder surface atoms. The SFE converges for all surfaces, hydrophobic and hydrophilic, as ions alter electrochemical properties of the surface via atomic and electronic displacements.
ContributorsXing, Qian (Author) / Herbots, Nicole (Thesis advisor) / Culbertson, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Treacy, Michael (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2011
Description
Lonsdaleite, also called hexagonal diamond, has been widely used as a marker of asteroidal impacts. It is thought to play a central role during the graphite-to-diamond transformation, and calculations suggest that it possesses mechanical properties superior to diamond. However, despite extensive efforts, lonsdaleite has never been produced or described as a separate, pure material. Here we show that defects in cubic diamond provide an explanation for the characteristic d-spacings and reflections reported for lonsdaleite. Ultrahigh-resolution electron microscope images demonstrate that samples displaying features attributed to lonsdaleite consist of cubic diamond dominated by extensive {113} twins and {111} stacking faults. These defects give rise to nanometre-scale structural complexity. Our findings question the existence of lonsdaleite and point to the need for re-evaluating the interpretations of many lonsdaleite-related fundamental and applied studies.
ContributorsNemeth, Peter (Author) / Garvie, Laurence (Author) / Aoki, Toshihiro (Author) / Dubrovinskaia, Natalia (Author) / Dubrovinsky, Leonid (Author) / Buseck, Peter (Author) / Department of Chemistry and Biochemistry (Contributor) / College of Liberal Arts and Sciences (Contributor) / School of Earth and Space Exploration (Contributor) / Center for Meteorite Studies (Contributor) / Ira A. Fulton Schools of Engineering (Contributor) / LeRoy Eyring Center for Solid State Science (Contributor) / School of Molecular Sciences (Contributor)
Created2014-11-01
Description
Interdigitated back contact (IBC) solar cells have achieved the highest single junction silicon wafer-based solar cell power conversion efficiencies reported to date. This thesis is about the fabrication of a high-efficiency silicon heterojunction IBC solar cell for potential use as the bottom cell for a 3-terminal lattice-matched dilute-nitride Ga (In)NP(As)/Si monolithic tandem solar cell. An effective fabrication process has been developed and the process challenges related to open circuit voltage (Voc), series resistance (Rs), and fill factor (FF) are experimentally analyzed. While wet etching, the sample lost the initial passivation, and by changing the etchant solution and passivation process, the voltage at maximum power recovered to an initial value of over 710 mV before metallization. The factors reducing the series resistance loss in IBC cells were also studied. One of these factors was the Indium Tin Oxide (ITO) sputtering parameters, which impact the conductivity of the ITO layer and transport across the a-Si:H/ITO interface. For the standard recipe, the chamber pressure was 3.5 mTorr with no oxygen partial pressure, and the thickness of the ITO layer in contact with the a-Si:H layers, was optimized to 150 nm. The patterning method for the metal contacts and final annealing also change the contact resistance of the base and emitter stack layers. The final annealing step is necessary to recover the sputtering damage; however, the higher the annealing time the higher the final IBC series resistance. The best efficiency achieved was 19.3% (Jsc = 37 mA/cm2, Voc = 691 mV, FF = 71.7%) on 200 µm thick 1-15 Ω-cm n-type CZ C-Si with a designated area of 4 cm2.
ContributorsMoeini Rizi, Mansoure (Author) / Goodnick, Stephen (Thesis advisor) / Honsberg, Christina (Committee member) / Goryll, Michael (Committee member) / Smith, David (Committee member) / Bowden, Stuart (Committee member) / Arizona State University (Publisher)
Created2022
Description
The future will be replete with Artificial Intelligence (AI) based agents closely collaborating with humans. Although it is challenging to construct such systems for real-world conditions, the Intelligent Tutoring System (ITS) community has proposed several techniques to work closely with students. However, there is a need to extend these systems outside the controlled environment of the classroom. More recently, Human-Aware Planning (HAP) community has developed generalized AI techniques for collaborating with humans and providing personalized support or guidance to the collaborators. In this thesis, the take learning from the ITS community is extend to construct such human-aware systems for real-world domains and evaluate them with real stakeholders. First, the applicability of HAP to ITS is demonstrated, by modeling the behavior in a classroom and a state-of-the-art tutoring system called Dragoon. Then these techniques are extended to provide decision support to a human teammate and evaluate the effectiveness of the framework through ablation studies to support students in constructing their plan of study (\ipos). The results show that these techniques are helpful and can support users in their tasks. In the third section of the thesis, an ITS scenario of asking questions (or problems) in active environments is modeled by constructing questions to elicit a human teammate's model of understanding. The framework is evaluated through a user study, where the results show that the queries can be used for eliciting the human teammate's mental model.
ContributorsGrover, Sachin (Author) / Kambhampati, Subbarao (Thesis advisor) / Smith, David (Committee member) / Srivastava, Sidhharth (Committee member) / VanLehn, Kurt (Committee member) / Arizona State University (Publisher)
Created2022
Description
Written corrective feedback (WCF) has received considerable attention in secondlanguage (L2) writing research. The conducive role of WCF in developing L2 writing and
second language acquisition has been corroborated by a number of theoretical frameworks,
and the findings of empirical studies, meta-analyses, and research syntheses. WCF research
has predominantly addressed its effectiveness in improving learners’ syntactic, lexical, and
orthographic knowledge. This dissertation project extends the scope of this line of research
to formulaic aspects of language and investigates the relative effectiveness of WCF
targeting formulaic vs. non-formulaic constructions in L2 writing. The text-analytic
descriptive aspect of this research design aimed at investigating the extent of L2 learners’
non-target-like use of formulaic vs. non-formulaic forms in L2 writing and writing
teachers’ WCF treatment of non-target (non)formulaic language use. A total of 480 first
drafts of essays written by 33 advanced adult English-as-a-foreign language (EFL) learners
during one semester and 480 drafts of essays corrected through WCF by three EFL teachers
constituted the corpus in this study. Advancing the field of learner corpus research, the
findings demonstrated that whereas learners’ non-target formulaic forms outnumbered that
of non-formulaic ones in their writing assignments, all three teachers provided WCF more
often for erroneous use of non-formulaic forms. The quasi-experimental aspect of the
research design attempts to add new empirical evidence on the L2 learning potential of
accessing and processing WCF provided for formulaic vs. non-formulaic constructions in
L2 writing. To this end, a total of 66 EFL learners in a Test of English as a Foreign
Language preparation course participated in a pretest-posttest design, with 5 experimental groups (those who were provided with direct, indirect, direct plus metalinguistic, and
indirect plus metalinguistic WCF) and a control group (those who were not provided with
WCF). Maintaining a division between formulaic vs. non-formulaic forms, the findings
provide empirical evidence on the interactions between types of WCF, types of linguistic
targets, and the effectiveness of WCF in terms of enhancing L2 learners’ accuracy and
acquisition in their revised writing and new writings in the short and long term.
ContributorsGholami, Leila (Author) / Smith, David (Thesis advisor) / Matsuda, Paul K (Committee member) / James, Mark A (Committee member) / Arizona State University (Publisher)
Created2022
Description
Transitioning into civilian life after military service is a challenging prospect. It can be difficult to find employment and maintain good mental health, and up to 70 percent of veterans experience homelessness or alcoholism. Upon discharge, many veterans pursue higher education as a way to reintegrate into civilian society. However, many studies have shown that veterans encounter multiple challenges during their attempt to reintegrate into civilian life, including anxiety, a lack of relevant skills, post-traumatic stress disorder (PTSD), and other issues that may lead to communication and interaction challenges in the higher education environment. Student veterans also face challenges in the lack of common language and culture clashes due to differences between military and college culture. This study used a mixed-methods approach to examine the challenges military veterans face related to language use in civilian life. The data was collected from 149 student veterans who completed a questionnaire and 11 student veterans who participated in interviews. Detailed analysis of collected data showed that student veterans experienced some challenges in language use, especially when they initially enrolled in their courses, but they seemed to have overcome challenges after spending time in the university setting. The veterans who had prior college education before joining the military seemed to have a slight advantage, having had experience using the academic language. The study also explored how student veterans chose to share their veteran status with other people in their university community. The findings showed that they strongly identified with their veteran identity and was comfortable sharing their status with others, but they also sometimes were reluctant to share their military experience in details because they were afraid that their peers would not understand.
ContributorsObaid, Naji (Author) / Matsuda, Aya (Thesis advisor) / Smith, David (Committee member) / James, Mark (Committee member) / Arizona State University (Publisher)
Created2022
Description
Studying the so-called ”hidden” phases of quantum materials—phases that do not exist under equilibrium conditions, but can be accessed with light—reveals new insights into the broader field of structural phase transitions. Using terahertz irradiation as well as hard x-ray probes made available by x-ray free electron lasers (XFELs) provides unique capabilities to study phonon dispersion in these materials. Here, we study the cubic peak of the quantum paraelectric strontium titanate (SrTiO3, STO) below the 110 K cubic-to-tetragonal tran- sition. Our results reveal a temperature and field strength dependence of the transverse acoustic mode in agreement with previous work on the avoided crossing occurring at finite wavevector, as well as evidence of anharmonic coupling between transverse optical phonons and a fully symmetric A1g phonon. These results elucidate previous optical studies on STO and hold promise for future studies on the hidden metastable phases of quantum materials.
ContributorsStanton, Jade (Author) / Teitelbaum, Samuel (Thesis director) / Smith, David (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Department of Physics (Contributor)
Created2023-05
Description
In this dissertation, the surface interactions of fluorine were studied during atomic layer deposition (ALD) and atomic layer etching (ALE) of wide band gap materials. To enable this research two high vacuum reactors were designed and constructed for thermal and plasma enhanced ALD and ALE, and they were equipped for in-situ process monitoring. Fluorine surface interactions were first studied in a comparison of thermal and plasma enhanced ALD (TALD and PEALD) of AlF3 thin films prepared using hydrogen fluoride (HF), trimethylaluminum (TMA), and H2-plasma. The ALD AlF3 films were compared ¬in-situ using ellipsometry and X-ray photoelectron spectroscopy (XPS). Ellipsometry showed a growth rate of 1.1 Å/ cycle and 0.7 Å/ cycle, at 100°C, for the TALD and PEALD AlF3 processes, respectively. XPS indicated the presence of Al-rich clusters within the PEALD film. The formation of the Al-rich clusters is thought to originate during the H2-plasma step of the PEALD process. The Al-rich clusters were not detected in the TALD AlF3 films. This study provided valuable insight on the role of fluorine in an ALD process.
Reactive ion etching is a common dry chemical etch process for fabricating GaN devices. However, the use of ions can induce various defects, which can degrade device performance. The development of low-damage post etch processes are essential for mitigating plasma induced damage. As such, two multistep ALE methods were implemented for GaN based on oxidation, fluorination, and ligand exchange. First, GaN surfaces were oxidized using either water vapor or O2-plasma exposures to produce a thin oxide layer. The oxide layer was addressed using alternating exposures of HF and TMG, which etch Ga2O3 films. Each ALE process was characterized using in-situ using ellipsometry and XPS and ex-situ transmission electron microscopy (TEM). XPS indicated F and O impurities remained on the etched surfaces. Ellipsometry and TEM showed a slight reduction in thickness. The very low ALE rate was interpreted as the inability of the Ga2O3 ALE process to fluorinate the ordered surface oxide on GaN (0001).
Overall, these results indicate HF is effective for the ALD of metal fluorides and the ALE of metal oxides.
ContributorsMessina, Daniel C (Author) / Nemanich, Robert J (Thesis advisor) / Goodnick, Stephen (Committee member) / Ponce, Fernando A (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2021