Thesis (PhD (Physics))--University of Stellenbosch, 2002. / Includes bibliography. / ENGLISH ABSTRACT: High temperature superconductivity is an important topic in contemporary solid state physics, and an area of very active research. Due to it’s potential for application in low temperature electronic devices, the material has attracted the attention of researchers in the electronic engineering and material science fields alike. Moreover, from a fundamental point of view, several questions remain unanswered, related to the origin of superconductivity of this class of materials and the nature of quantised magnetic flux present in magnetised samples. In this work, flux creep phenomena in a thin superconducting YBa₂Cu₃O₇ film deposited by pulsed laser deposition, is investigated near the critical temperature 0 ≤ Tc – T ≤ 10 K. Creep activation energy U0 and critical current density jc were determined as a function of temperature close to Tc, providing important data to a problem of high-Tc superconductivity which is still a matter of debate. In particular it is still an open question whether restoring the temperature in a creep freezing experiment in fact restores the film to it's original state before the freezing. The most important novel results concern the regime of critical fluctuations in the vicinity Tc - T < 1 K. We studied the isothermal relaxation of trapped magnetic flux, and determined that the long time decay follows a power law, where the exponent is inversely proportional to the creep activation energy. The temperature dependence of the critical current density jc(T) of the YBa₂Cu₃O₇ film close to Tc was obtained during warming runs. It was determined that jc(T) follows a square root dependence on T to high accuracy in the range 0.2 ≤ Tc – T ≤ 1.5 K. During flux creep experiments an interesting phenomenon called creep freezing related to the strong temperature dependence of the relaxation rate was observed. A pronounced slowing of relaxation with only a small drop in temperature from a starting temperature close to Tc was detected. Experiments were conducted by initiating an isothermal flux decay run. At a certain point the temperature was slightly lowered, and the flux decay stopped within experimental accuracy. When the temperature was restored to the initial value, the flux decay resumed at the previous rate before cooling. An argument based on vortex drift velocity was employed to explain the phenomenon qualitatively. During the course of this investigation, a pulsed laser deposition (PLD) system was designed and built from scratch. PLD involves the interaction of a focussed laser pulse with a multielemental solid target material. Material ablated from the target forms a fast moving plume consisting of atomic and molecular particles, directed away from the target, and towards a usually heated substrate on which the particles condense layer by layer to form a thin film. The substrate temperature and background gas are carefully controlled to be conductive to the growth of a desired phase of the multi-elemental compound. The PLD system proved to be quite versatile in the range of materials that could be deposited. It was used to deposit thin films of different materials, most notable were good quality superconducting YBa₂Cu₃O₇, thermochromic VO2, and magnetoresistive LaxCa1-xMnO3. Metallic Au and Ag layers were also successfully deposited on YBa2Cu3O7 thin films, to serve as protective coatings. The critical temperatures of the best superconducting films were 90 K as determined by resistivity measurement. The optimal deposition conditions to deposit high quality superconducting YBa₂Cu₃O₇ thin films was found to be: deposition temperature 780°C, laser energy density 2-3 J/cm2, oxygen partial pressure 0.2 mbar, and target-substrate distance 35 mm. This yields film with Tc ~ 90 K. It was found that deposition temperature plays the predominant role in determining the quality of YBa₂Cu₃O₇ thin films deposited by PLD. / AFRIKAANSE OPSOMMING: Hoë temperatuur supergeleiding is tans ’n aktuele onderwerp van vastetoestandfisika en dit is ’n gebied van baie aktiewe navorsing. Weens die potensiaal vir toepassings van hoë temperatuur supergeleiers in elektronika, het dié klas materiale die aandag van fisici and elektronici getrek. Verskeie fundamentele vraagstukke bly steeds onbeantwoord, veral met betrekking tot die oorsprong van supergeleiding in hierdie materiale en die gedrag van gekwantiseerde magnetiese vloed (“vortekse”) in gemagnetiseerde monsters. In hierdie werk word diffusie van vortekse in dun supergeleidende YBa₂Cu₃O₇ films ondersoek naby die kritieke temperatuur (0 ≤ Tc - T ≤ 10 K). Die temperatuur afhanklikheid van die diffusie aktiveringsenergie U0 en die kritieke stroomdigtheid jc word bepaal naby Tc. Dit verskaf belangrike inligting tot probleme in hoë temperatuur supergeleiding wat tans nog onbeantwoord bly. In die besonder is dit steeds ’n ope vraag of die herstel van die aanvanklike temperatuur in ’n vloedstollings eksperiment waarlik die film tot die oorspronklike toestand herstel. Die belangrikste nuwe resultate hou verband met die gebied van kritieke fluktuasies van die orde parameter in die omgewing 0 < Tc - T < 1 K. Ons het die isotermiese ontspanning van vortekse verstrik in die kristalstruktuur bestudeer, en bepaal dat die lang tydsverval ’n magsverwantskap handhaaf, waar die eksponent omgekeerd eweredig is aan U0. Die temperatuur afhanklikheid van die kritieke stroomdigtheid jc(T) van die YBa₂Cu₃O₇ film naby Tc is bepaal tydens verhittingslopies. Daar is bevind dat naby Tc, jc ’n vierkantswortel verband met T volg, tot hoë noukeurigheid in die gebied 0.2 ≤ Tc – T ≤ 1.5 K. Gedurende vorteksdiffusie eksperimente is ’n interessante verskynsel naamlik vloedstolling (“flux freezing”) waargeneem. Dit hou verband met die sterk temperatuur afhanklikheid van die vervaltempo van die magnetiese moment van ’n gemagnetiseerde film. ’n Skerp daling van die vervaltempo, weens slegs ’n klein temperatuurdaling vanaf die begin temperatuur naby Tc, is waargeneem. Gedurende eksperimente is daar aanvanklik ’n isotermiese vloedontspanning teweeg gebring. Op ’n sekere tydstip is die temperatuur effens verlaag, waarby die vloedontspanning tot stilstand gekom het binne grense van waarneming. Wanneer die temperatuur weer herstel is na die oorspronklike, het die vloedontspanning voortgegaan teen die tempo voor die temperatuurverlaging. ’n Verklaring wat gebaseer is op vorteks dryfsnelheid was aan die hand gedoen om hierdie gedrag te verklaar. ’n Groot komponent van die projek was om die dun YBa₂Cu₃O₇ films self te vervaardig. Tydens hierdie ondersoek, is ’n gepulseerde laser deposisie (“PLD”) sisteem eiehandig ontwerp en gebou. PLD behels die interaksie van ’n gefokuseerde laser puls met ’n teiken bestaande uit ’n multi-element vastestofverbinding. Materiaal wat verdamp (“ablate”) word, vorm ’n snelbewegende pluim bestaande uit atomiese en molekulêre deeltjies. Dit beweeg vanaf die teiken na ’n verhitte substraat, waarop die deeltjies kondenseer om laag vir laag ’n dun film te vorm. Die substraat temperatuur en agtergrond gas word sorgvuldig beheer om die groei van die verlangde fase van die multi-element verbinding teweeg te bring. Die PLD sisteem is baie veeldoelig ten opsigte van die verskeidenheid materiale wat suksesvol neergeslaan kan word. Dit was aangewend om verskillende materiale neer te slaan, onder andere supergeleidende YBa₂Cu₃O₇, termochromiese VO2, en magnetoresistiewe LaxCa1-xMnO3. Geleidende Au en Ag lagies is ook suksesvol neergeslaan op YBa₂Cu₃O₇ dun films, om te dien as beskermingslagies. Die kritieke temperatuur van die beste supergeleidende films was 90 K soos bepaal deur weerstandsmetings. Die optimale neerslaan toestand vir hoë kwaliteit YBa₂Cu₃O₇ dun films was: substraat temperatuur 780°C, laser energiedigtheid 2 - 3 J/cm2, suurstofdruk 0.2 mbar, en teiken-substraat afstand 35 mm. Daar is bevind dat die substraat temperatuur die deurslaggewende rol speel tydens die neerslaan proses om die kwaliteit van die supergeleidende films te bepaal.

Thesis (MEng (Electrical and Electronic Engineering))--University of Stellenbosch, 2006. / The Josephson effect of high-temperature superconducting nanobridge structures is studied worldwide. Until now, nanobridges are generally fabricated with focused ion beam milling on planar thin films. These nanobridges are employed as weak links in superconducting quantum interference devices (SQUIDs) and used in superconducting flux flow transistors and devices. This project had two main objectives: to improve the sidewall angle of photoresist lines, with the aid of atomic force microscopy (AFM) nanolithography; and to fabricate hightemperature Josephson junctions by constricting superconductive YBCO lines on MgO substrates with AFM nanolithography. The entire fabrication process is explained including photolithography, deposition of the YBCO thin films with pulsed laser deposition (PLD), nanolithography and wet etching. Although the testing of the junctions did not show any Josephson behaviour, it could be demonstrated that nanobridge structures can successfully be created by AFM nanolithography. The entire fabrication process has been demonstrated in detail for the benefit of future research.

<p>Thin film deposition techniques are indispensable to the development of modern technologies as thin film based optical coatings, optoelectronic devices, sensors, and biological implants are the building blocks of many complicated technologies, and their performance heavily depends on the applied deposition technique. Particularly, the emergence of novel solution-processed materials, such as soft organic molecules, inorganic compounds and colloidal nanoparticles, facilitates the development of flexible and printed electronics that are inexpensive, light weight, green and smart, and these thin film devices represent future trends for new technologies. One appealing feature of solution-processed materials is that they can be deposited into thin films using solution-processed deposition techniques that are straightforward, inexpensive, high throughput and advantageous to industrialize thin film based devices. However, solution-processed techniques rely on wet deposition, which has limitations in certain applications, such as multi-layered film deposition of similar materials and blended film deposition of dissimilar materials. These limitations cannot be addressed by traditional, vacuum-based deposition techniques because these dry approaches are often too energetic and can degrade soft materials, such as polymers, such that the performance of resulting thin film based devices is compromised.</p><p>The work presented in this dissertation explores a novel thin film deposition technique, namely emulsion-based, resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE), which combines characteristics of wet and dry deposition techniques for solution-processed materials. Previous studies have demonstrated the feasibility of emulsion-based RIR-MAPLE to deposit uniform and continuous organic, nanoparticle and blended films, as well as hetero-structures that otherwise are difficult to achieve. However, fundamental understanding of the growth mechanisms that govern emulsion-based RIR-MAPLE is still missing, which increases the difficulty of using rational design to improve the performance of initial RIR-MAPLE devices that have been demonstrated. As a result, it is important to study the fundamentals of emulsion-based RIR-MAPLE in order to provide insight into the long-term prospects for this thin film deposition technique.</p><p>This dissertation explores the fundamental deposition mechanisms of emulsion-based RIR-MAPLE by considering the effects of the emulsion target composition (namely, the primary solvent, secondary solvent, and surfactant) on the properties of deposited polymer films. The study of primary solvent effects on hydrophobic polymer deposition helps identify the unique method of film formation for emulsion-based RIR-MAPLE, which can be described as cluster-by-cluster deposition of emulsified particles that yields two levels of ordering (i.e., within the clusters and among the clusters). The generality of this film formation mechanism is tested by applying the lessons learned to hydrophilic polymer deposition. Based on these studies, the deposition design rules to achieve smooth polymer films, which are important for different device applications, are identified according to the properties of the polymer.</p><p>After discussion of the fundamental deposition mechanisms, three applications of emulsion-based RIR-MAPLE, namely thin film deposition of organic solar cells, polymer/nanoparticle hybrid solar cells, and antimicrobial/fouling-release multifunctional films, are studied. The work on organic solar cells identifies the ideal deposition mode for blended films with nanoscale domain sizes, as well as demonstrates the relationships among emulsion target composition, film properties, and corresponding device performance. The studies of polymer/nanoparticle hybrid solar cells demonstrate precise control of colloidal nanoparticle deposition, in which the integrity of nanoparticles is maintained and a distinct film morphology is achieved when co-deposited with polymers. Finally, the application of antimicrobial and fouling-release multifunctional films demonstrates the importance of blended film deposition with nanoscale phase separation, a key feature to achieving reusable bio-films that can kill bacteria when illuminated with ultraviolet light.</p><p>Thus, this dissertation provides great insight to the fundamentals of emulsion-based RIR-MAPLE, serves as a valuable reference for future development, and paves the pathway for wider adoption of this unique thin film deposition technique, especially for organic solar cells.</p> / Dissertation

Pulsed laser flash photolysis with both visible and infrared detection has been applied to the study of the displacement of weakly coordinating ligands (Lw) by strongly "trapping" nucleophiles (Ls) containing either an olefinic functionality (Ls = 1-hexene, 1-decene, 1-tetradecene) or nitrogen (Ls = acetonitrile, hydrocinnamonitrile) from the photogenerated 16 electron pentacarbonylchromium (0) intermediate. 5-Chloropent-l-ene (Cl-ol), a potentially bidentate ligand, has been shown to form (ol-Cl) pentacarbonylchromium (0), in which Cl-ol is bonded to Cr via a lone pair on the chlorine, and isomerize to (Cl-ol) pentacarbonylchromium (0), in which Cl-ol is bonded to the olefinic functionality on the submillisecond time scale. This process has been studied in both the infrared and visible region employing both fluorobenzene or n-heptane as the "inert" diluent. Parallel studies employing 1-chlorobutane and 1-hexene were also evaluated and showed great similiarity with the Cl-ol system. The data supported a largely dissociative process with a possibility of a small interchange process involving the H's on the alkyl chain. Studies were also carried out for various Cr(CO)6/arene/Ls systems (arene = various alkyl or halogenated substituted benzenes). The data indicated that for both C6H5R (R=various alkyl chains) or multi-alkyl substituted arenes (i.e. o-xylene, 1,2,3-trimethylbenzene) containing an "unhindered" ring-edge, bonding to the the Cr(CO)5 moiety occurs "edge on" via a partially delocalized center of unsaturation on the ring. The data indicated that both electronic and steric properties of the arenes influence the kinetics, and that an interchange pathway takes place at least, in part, through the alkyl chains on both the arenes and "trapping" nucleophiles. Moreover, halogenated arenes bond through the lone pair on the halogen for both CI- and Br- derivatives but "edge-on" for the fluorinated arenes. Finally, in the case of arene complexes without and "unhindered" ring-edge (i.e., 1,2,3,4,5-pentamethylbenzene) bonding can occur either "edge-on" or through the ring center of the arene or combination of the two. Carbonyl stretching frequencies for the arenes are also indicative of the type of bonding.

We measured the diffraction efficiency response of two photorefractive polymer devices according to the duration of the single laser pulse used to record the hologram. The pulse duration was varied from 6 nanoseconds to 1 second, while the pulse energy density was maintained constant at 30 mJ/cm(2). This changed the peak power from 5 x 10(9) mW to 30 mW. We observed a strong reciprocity failure of the efficiency according to the pulse duration, with a reduction as large as a factor 35 between 1 second and 30 mu s pulse duration. At even lower pulse duration (< 30 mu s), the efficiency leveled out and remained constant down to the nanosecond exposure time. The same behavior was observed for samples composed of the same material but with and without buffer layers deposited on the electrodes, and different voltages applied during the holographic recording. We explained these experimental results based on the charge transport mechanism involved in the photorefractive process. The plateau is attributed to the single excitation of the charge carriers by short pulses (T-p < 30 mu s). The increase of efficiency for longer pulse duration (T-p > 30 mu s) is explained by multiple excitations of the charge carriers that allows longer distance to be traveled from the excitation sites. This longer separation distance between the carriers increases the amplitude of the space-charge field, and improves the index modulation. The understanding of the response of the diffraction efficiency according to the pulse duration is particularly important for the optimization of photorefractive materials to be used at high refresh rate such as in videorate 3D display.

My dissertation research focuses on the investigation of the transport and magnetic properties of transition metal and rare earth doped oxides, particularly SnO2 and HfO2 thin films. Cr- and Fe-doped SnO2 films were deposited on Al2O3 substrates by pulsed-laser deposition. Xray- diffraction patterns (XRD) show that the films have rutile structure and grow epitaxially along the (101) plane. The diffraction peaks of Cr-doped samples exhibit a systematic shift toward higher angles with increasing Cr concentration. This indicates that Cr dissolves in SnO2. On the other hand, there is no obvious shift of the diffraction peaks of the Fe-doped samples. The magnetization curves indicate that the Cr-doped SnO2 films are paramagnetic at 300 and 5 K. The Fe-doped SnO2 samples exhibit ferromagnetic behaviour at 300 and 5 K. Zero-field-cooled and field-cooled curves indicate super paramagnetic behavior above the blocking temperature of 100 K, suggesting that it is possible that there are ferromagnetic particles in the Fe-doped films. It was found that a Sn0.98Cr0.02O2 film became ferromagnetic at room temperature after annealing in H2. We have calculated the activation energy and found it decreasing with the annealing, which is explained by the increased oxygen vacancies/defects due to the H2 treatment of the films. The ferromagnetism may be associated with the presence of oxygen vacancies although AMR was not observed in the samples. Pure HfO2 and Gd-doped HfO2 thin films have been grown on different single crystal substrates by pulsed laser deposition. XRD patterns show that the pure HfO2 thin films are of single monoclinic phase. Gd-doped HfO2 films have the same XRD patterns except that their diffraction peaks have a shift toward lower angles, which indicates that Gd dissolves in HfO2. Transmission electron microscopy images show a columnar growth of the films. Very weak ferromagnetism is observed in pure and Gd-doped HfO2 films on different substrates at 300 and 5 K, which is attributed to either impure target materials or signals from the substrates. The magnetic properties do not change significantly with post deposition annealing of the HfO2 films.

ABSTRACT The focus of this work was the study possible ways to improve the efficiency of solar cells. To this end, the main aim was to investigate the deposition process of Indium Tin Oxide (ITO), Titanium Dioxide (TiO2), multi-layers ITO/TiO2 on quartz SiO2 substrates under different conditions (oxygen pressure, laser fluence and wavelength, and temperature) and later gold nanoparticles by the Reactive Pulsed Laser Ablation Deposition (RPLAD) technique. It was intended to investigate their electrical structural and optical properties under selected conditions for possible application to Dye Sensitised Solar Cells (DSSC). Under optimised conditions, maximum deposition rates of 12nm/min for ITO and 21nm/min for TiO2 thin films were achieved. Rutherford Backscattering Spectrometry (RBS) with 2MeV He+ ions was used to measure the films thickness. Uniform thicknesses over a large area were found to be about 400nm and 800nm for ITO and TiO2 films, respectively. Crystalline properties were studied via x-ray diffraction and Raman spectroscopy. X-ray Diffraction (XRD) analysis revealed that the ITO films are highly orientated nanocrystals with their a-axis normal to the glass substrate surface. The average particle size of the precipitated nanocrystals was calculated to be 10-15nm. The structure of the films was characterised via Atomic Force Microscopy (AFM) imaging of the top surface of the film. The films have a rough surface with average roughness of 26-30nm. Pores were observed with a density of 144 and 125 pores/mm2 and average size of 150 and 110nm for ITO films deposited at 200 and 400°C, respectively. TiO2 films deposited on the prepared ITO films were less crystalline. Annealing was performed at 300 and 500°C for 3 consecutive hours and the XRD results show that the transformation of TiO2 film into anatase phase was almost complete with a crystal size of ~ 6-7nm. Scanning Transmission Electron Microscopy (STEM) of the surfaces was also performed. The TiO2 films deposited onto the prepared ITO films present a relatively high pore size with an average pore diameter of ~ 40nm and excellent uniformity. It is interesting to note that the pores are randomly arranged. The random arrangement of the pores network may actually be beneficial for producing a uniform electrode. In addition, STEM cross-sectional analysis of the films showed a columnar structure but no evidence of voids in the structure. The large surface area produced suggests applications in DSSC. The electrical properties of the films were investigated and an estimation of resistivity and Hall mobility was made. Low values of resistivity and high values of mobility were observed for ITO films. The resistivity of the film increases with increasing thickness while it decreases when increasing the deposition temperature. The lowest value was found to be 1.5x10-6Ωm for ITO films deposited at 400°C. Hall mobility was found to increase with substrate temperature. In this investigation, the highest Hall mobility at room temperature was estimated to be 22.3cm2/Vs under ambient O2 pressure (PO2) of 1Pa and 52.1 and 51.3cm2/Vs for films deposited at 200 and 400°C, respectively. But the best ITO film was deposited at 200°C, since this film combines good resistivity, good Hall mobility and good transmittance. UV-VIS-IR transmission spectra were recorded on a Perkin Elmer Lambda 900. From the transmission data, the energy gap as well as the optical constant was estimated. A high transmission for ITO films in the visible (Vis) range was observed which was above 88% for films produced at room temperature and above 95% for those deposited at 200°C. The transmission for the films produced in oxygen was about 90% above 400nm, whereas it lies between 70 and 80% for films produced in rare gases. An increase in the band gap was observed by increasing the oxygen pressure and substrate temperature for ITO films. Increasing the quartz SiO2 substrate temperature from room temperature to 400 °C resulted in an increase of the transmission of TiO2 films, mostly in the Visible Near Infrared (Vis-NIR) from about 70% to 92%. After annealing at 500°C for 3 consecutive hours, the transmission of TiO2 film further sharply decreases toward shorter wavelengths. Analysis of the transmittance curve of TiO2/Au shows a decrease of about 6% of the transmission in the Ultraviolet Visible (UV-Vis) range. Optical absorption edge analysis showed that the optical density could be used to detect the film growth conditions and to correlate the film structure and the absorption edge. The TiO2 films deposited present a direct band gap at 3.51eV and 3.37eV for TiO2 as deposited and after annealing, respectively, while the indirect band gap was found to be 3.55eV and 3.26eV for TiO2 films as deposited and after annealing, respectively. There was a shift of about 0.1eV between as deposited ITO monolayer films and ITO/TiO2 bilayers deposited at 200°C. A small shift towards shorter wavelengths has been observed for multilayer ITO/TiO2/Au. In this case, the increase of Eg was ascribed to a reduction of the oxygen vacancies with increasing substrate temperature at which the ITO film was deposited. The change in the shape of the fundamental absorption edge is considered to reflect the variation of density and the short range structural modifications undetected by structural characterisations. Enlargement of band-gap energies of semiconductors may be advantageous when used in DSSC to suppress the charge recombination between the reduced electrolytes and the photo-excited holes in the valence band of TiO2 substrates and enhance the open-circuit potential of the cell. When ITO/TiO2 bilayers were annealed before depositing Au, the gap energy remained constant.

Hydrogen exposure of insulating d0-titanates, such as SrTiO3 (STO), has displayed the formation of intriguing conducting states. These conducting states form through the use of forming gas (N2/H2) annealing or hydrogen plasma exposure, where hydrogen gas is exposed to high energy microwaves. The exposure of STO to hydrogen causes metallic conductivity due to the introduction of hydrogen cations on some of the oxygen sites. However, the optical properties of this hydrogen-exposed STO have not been well-studied. Further, Ba0.5Sr0.5TiO3 (BST), an insulating dielectric, also shows changes in its conductivity upon hydrogen exposure. Unlike STO where the conductivity of the hydrogen-exposed material has been characterized, the optical, electronic, and transport properties of hydrogen exposed BST have not been studied. Thus, by studying hydrogen-exposed BST and STO, our understanding of the effects of hydrogen on insulators can be enhanced. In the first study, the effects of the exposure of insulating dielectric BST thin films to a hydrogen plasma is presented. These BST thin films are deposited on GdScO3 (GSO) substrates via Pulsed Laser Deposition (PLD). After deposition, the thin films are exposed to a hydrogen plasma. Just five minutes of hydrogen plasma exposure is enough to induce conductivity in the BST thin film. This conducting state is dominated by the interplay of disorder and strong electron correlations introduced during hydrogen exposure. Further, the optical properties indicate the formation of a transparent conductor, as the introduction of disorder and strong correlations has not changed the optical properties of the BST thin film in the visible spectrum. BST demonstrates an example of a new type of transparent conductor that utilizes large effective mass carriers to generate conductivity. In the second study, the effects of hydrogen doping on the surface of STO is explored. The conducting heterointerface that forms between PLD-deposited thin films of LaAlO3 (LAO) on STO is used as the standard to explore this hydrogen surface doping. The optical, electronic, and transport properties of water-leached and buffered hydrofluoric acid (BHF) etched heterointerfaces are characterized and compared. The recently developed water-leaching method is compared with the well-known BHF etching method, which has been shown to unintentionally dope the STO surface with fluorine and hydrogen. Both methods generate single-terminated atomically flat STO substrate surfaces that are ideal for heterointerface formation. After deposition, the optical, electronic, and transport properties of both the water-leached and BHF-etched heterointerfaces show no meaningful difference, demonstrating that water-leaching may also unintentionally dope the STO substrate surface with hydrogen. However, these results confirm that water-leaching generates a high-quality conducting heterointerface without the safety concerns of BHF.

Transition metal oxides have attracted widespread attention due to their broad range of fascinating exotic phenomena such as multiferroicity, superconductivity, colossal magnetoresistance and metal-to-insulator transition. Due to the interplay between spin, charge, lattice and orbital degrees of freedom of strongly correlated d electrons, these physical properties are extremely sensitive to the external perturbations such as magnetic field, charge carrier doping and pressure, which provide a unique chance in search for novel exotic quantum states. Ruthenate systems are a typical strongly correlated system, with rich ordered states and their properties are extremely sensitive to external stimuli. Recently, the experimental observation of spin-orbit coupling induced Mott insulator in Sr2IrO4 as well as the theoretical prediction of topological insulating state in other iridates, have attracted tremendous interest in the physics of strong correlation and spin-orbit coupling in 4d/5d compounds. We observe an itinerant ferromagnetic ground state of Ca2RuO4 film in stark contrast to the Mott-insulating state in bulk Ca2RuO4. We have also established the epitaxial strain effect on the transport and magnetic properties for the (Ca,Sr)2RuO4 thin films. For Sr2IrO4 thin films, we will show that the Jeff = 1/2 moment orientation can be modulated by epitaxial strain. In addition, we discovered novel Ba7Ir3O13+x thin films which exhibit colossal permittivity. / acase@tulane.edu

High energy pulse laser peening (HEPLP) is a manufacturing process, in which a strong shock wave is produced and induces high pressures on the surface of the target material. Generally, this process is used to improve material properties such as the hardness and fatigue life. First a 2D multi-physics model for the process was investigated, which simulates the pressure induced on the surface of the target material. The model can be coupled with commercial finite element software, such as ABAQUS, to more accurately simulate the HEPLP process to find stresses and deformations on the surface. Next two novel applications using the HEPLP process were investigated. The first, laser shock bending is a sheet metal micro-forming process using HEPLP to accurately bend, shape, precision align, or repair micro-components with bending angles less than 10°. Negative bending angle (away from laser beam) can be achieved with the high-energy pulsed laser, in addition to the conventional positive laser bending mechanism. In this thesis, various experimental and numerical studies on aluminum sheets were conducted to investigate the different deformation mechanisms, positive and negative. The experiments were conducted with the sheet thickness varying from 0.25 to 1.75 mm and laser pulse energy of 0.2 to 0.5 J. A critical thickness threshold of 0.7-0.88 mm was found that the transition of positive negative bending mechanism occurs. A statistic regression analysis was also developed to determine the bending angle as a function of laser process parameters for positive bending cases. The second application studied used HEPLP to imprint complex two-dimensional (2D) patterns dental implant material of cpTi. Pure titanium (commercial pure cpTi) is an ideal dental implant material, without the leeching of toxic alloy elements. Evidence has shown that unsmooth implant surface topologies may contribute to the osteoblast differentiation in human mesenchymal pre-osteoblastic cells, which is helpful to avoid long-term peri-abutment inflammation issues for the dental implant therapy with transcutaneous devices. Studies have been conducted on the grit blasted, acid etched, or uni-directional grooved Ti surface, however, for these existing approaches the surface quality is difficult to control or may even damage the implant. The strong shock wave generated by HEPLP is used to press a stainless steel grid, used as a stamp, on Ti foils to imprint a 2D pattern. In this study, the multiple grid patterns and grid sizes were applied to test for cell-attachment improvements. Then, the cell culture tests were conducted with the patterned surface to investigate the contribution of these 2D patterns, with the control tests of the other existing implant surface topography forming approaches. The micro-patterns proved successful in increasing the cell-attachment, increasing the number of cells attaching to the material and also contributing to the cell-growth within the grooved areas.