The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Fabrication of a two-terminal super conducting device with a poled ferroelectric control layer

The discovery of High-Temperature Superconductors (HTSCs) has spurred the need for the fabrication of superconducting electronic devices able to match the performance of today's semiconductor devices. While there are several HTSCs in use today, YBaCuO7-x (YBCO) is the better characterized and more widely used material for small electronic applications. This thesis explores the fabrication of a Two-Terminal device with a superconductor and a painted on electrode as the terminals and a ferroelectric, BaTiO 3 (BTO), in between. The methods used to construct such a device and the challenges faced with the fabrication of a viable device will be examined. The ferroelectric layer of the devices that proved adequate for use were poled by the application of an electric field. Temperature Bias Poling used an applied field of 105V/cm at a temperature of approximately 135*C. High Potential Poling used an applied field of 106V/cm at room temperature (20*C). The devices were then tested for a change in their superconducting critical temperature, Tc. A shift of 1-2K in the Tc(onset) of YBCO was observed for Temperature Bias Poling and a shift of 2-6K for High Potential Poling. These are the first reported results of the field effect using BTO on YBCO. The mechanism involved in the shifting of Tc will be discussed along with possible applications.

Vocabulary Learning through Use of the Picture-Word Inductive Model for Young English Learners in China: A Mixed Methods Examination Using Cognitive Load Theory

English has been taught as a core and compulsory subject in China for decades. Recently, the demand for English in China has increased dramatically. China now has the world’s largest English-learning population. The traditional English-teaching method cannot continue to be the only approach because it merely focuses on reading, grammar and translation, which cannot meet English learners and users’ needs (i.e., communicative competence and skills in speaking and writing). This study was conducted to investigate if the Picture-Word Inductive Model (PWIM), a new pedagogical method using pictures and inductive thinking, would benefit English learners in China in terms of potential higher output in speaking and writing. With the gauge of Cognitive Load Theory (CLT), specifically, its redundancy effect, I investigated whether processing words and a picture concurrently would present a cognitive overload for English learners in China. I conducted a mixed methods research study. A quasi-experiment (pretest, intervention for seven weeks, and posttest) was conducted using 234 students in four groups in Lianyungang, China (58 fourth graders and 57 seventh graders as an experimental group with PWIM and 59 fourth graders and 60 seventh graders as a control group with the traditional method). No significant difference in the effects of PWIM was found on vocabulary acquisition based on grade levels. Observations, questionnaires with open-ended questions, and interviews were deployed to answer the three remaining research questions. A few students felt cognitively overloaded when they encountered too many writing samples, too many new words at one time, repeated words, mismatches between words and pictures, and so on. Many students listed and exemplified numerous strengths of PWIM, but a few mentioned weaknesses of PWIM. The students expressed the idea that PWIM had a positive effect on their English teaching. As integrated inferences, qualitative findings were used to explain the quantitative results that there were no significant differences of the effects of the PWIM between the experimental and control groups in both grade levels, from four contextual aspects: time constraints on PWIM implementation, teachers’ resistance, how to use PWIM and PWIM implemented in a classroom over 55 students.

Developing a Process to Create and Validate an Instrument Assessing Student Attainment of Competencies at an Intercultural University in Mexico

This study took place at one of the intercultural universities (IUs) of Mexico that serve primarily indigenous students. The IUs are pioneers in higher education despite their numerous challenges (Bertely, 1998; Dietz, 2008; Pineda & Landorf, 2010; Schmelkes, 2009). To overcome educational inequalities among their students (Ahuja, Berumen, Casillas, Crispín, Delgado et al., 2004; Schmelkes, 2009), the IUs have embraced performance-based assessment (PBA; Casillas & Santini, 2006). PBA allows a shared model of power and control related to learning and evaluation (Anderson, 1998). While conducting a review on PBA strategies of the IUs, the researcher did not find a PBA instrument with valid and reliable estimates. The purpose of this study was to develop a process to create a PBA instrument, an analytic general rubric, with acceptable validity and reliability estimates to assess students’ attainment of competencies in one of the IU’s majors, Intercultural Development Management. The Human Capabilities Approach (HCA) was the theoretical framework and a sequential mixed method (Creswell, 2003; Teddlie & Tashakkori, 2009) was the research design. IU participants created a rubric during two focus groups, and seven Spanish-speaking professors in Mexico and the US piloted using students’ research projects. The evidence that demonstrates the attainment of competencies at the IU is a complex set of actual, potential and/or desired performances or achievements, also conceptualized as “functional capabilities” (FCs; Walker, 2008), that can be used to develop a rubric. Results indicate that the rubric’s validity and reliability estimates reached acceptable estimates of 80% agreement, surpassing minimum requirements (Newman, Newman, & Newman, 2011). Implications for practice involve the use of PBA within a formative assessment framework, and dynamic inclusion of constituencies. Recommendations for further research include introducing this study’s instrument-development process to other IUs, conducting parallel mixed design studies exploring the intersection between HCA and assessment, and conducting a case study exploring assessment in intercultural settings. Education articulated through the HCA empowers students (Unterhalter & Brighouse, 2007; Walker, 2008). This study aimed to contribute to the quality of student learning assessment at the IUs by providing a participatory process to develop a PBA instrument.

Mixed Spatial and Nonspatial Problems in Location Based Services

With hundreds of millions of users reporting locations and embracing mobile technologies, Location Based Services (LBSs) are raising new challenges. In this dissertation, we address three emerging problems in location services, where geolocation data plays a central role. First, to handle the unprecedented growth of generated geolocation data, existing location services rely on geospatial database systems. However, their inability to leverage combined geographical and textual information in analytical queries (e.g. spatial similarity joins) remains an open problem. To address this, we introduce SpsJoin, a framework for computing spatial set-similarity joins. SpsJoin handles combined similarity queries that involve textual and spatial constraints simultaneously. LBSs use this system to tackle different types of problems, such as deduplication, geolocation enhancement and record linkage. We define the spatial set-similarity join problem in a general case and propose an algorithm for its efficient computation. Our solution utilizes parallel computing with MapReduce to handle scalability issues in large geospatial databases. Second, applications that use geolocation data are seldom concerned with ensuring the privacy of participating users. To motivate participation and address privacy concerns, we propose iSafe, a privacy preserving algorithm for computing safety snapshots of co-located mobile devices as well as geosocial network users. iSafe combines geolocation data extracted from crime datasets and geosocial networks such as Yelp. In order to enhance iSafe's ability to compute safety recommendations, even when crime information is incomplete or sparse, we need to identify relationships between Yelp venues and crime indices at their locations. To achieve this, we use SpsJoin on two datasets (Yelp venues and geolocated businesses) to find venues that have not been reviewed and to further compute the crime indices of their locations. Our results show a statistically significant dependence between location crime indices and Yelp features. Third, review centered LBSs (e.g., Yelp) are increasingly becoming targets of malicious campaigns that aim to bias the public image of represented businesses. Although Yelp actively attempts to detect and filter fraudulent reviews, our experiments showed that Yelp is still vulnerable. Fraudulent LBS information also impacts the ability of iSafe to provide correct safety values. We take steps toward addressing this problem by proposing SpiDeR, an algorithm that takes advantage of the richness of information available in Yelp to detect abnormal review patterns. We propose a fake venue detection solution that applies SpsJoin on Yelp and U.S. housing datasets. We validate the proposed solutions using ground truth data extracted by our experiments and reviews filtered by Yelp.