abstract: Transparent conductive oxides (TCOs) are used as electrodes for a number of optoelectronic devices including solar cells. Because of its superior transparent and conductive properties, indium (In) tin (Sn) oxide (ITO) has long been at the forefront for TCO research activities and high-volume product applications. However, given the limited supply of In and potential toxicity of Sn-based compounds, attention has shifted to alternative TCOs like ZnO doped with group-III elements such as Ga and Al. Employing a variety of deposition techniques, many research groups are striving to achieve resistivities below 1E-4 ohm-cm with transmittance approaching the theoretical limit over a wide spectral range. In this work, Ga-doped ZnO is deposited using pulsed laser deposition (PLD). Material properties of the films are characterized using a number of techniques. For deposition in oxygen at pressures >1 mTorr, post-deposition annealing in forming gas (FG) is required to improve conductivity. At these higher oxygen pressures, thermodynamic analysis coupled with a study using the Hall effect measurements and photoluminescence spectroscopy suggest that conductivity is limited by oxygen-related acceptor-like defects in the grains that compensate donors, effectively reducing the net carrier concentration and creating scattering centers that reduce electron mobility. Oxygen is also responsible for further suppression of conductivity by forming insulative metal oxide regions at the grain edges and oxygen-related electron traps at the grain boundaries. The hydrogen component in the FG is thought to passivate the intra-grain acceptor-like defects and improve carrier transport across these grain boundaries. Given this deleterious effect of oxygen on conductivity, depositions are performed in pure argon (Ar), i.e., the only oxygen species in the growth ambient are those ejected directly from the PLD solid source target. Ga-doped ZnO deposited in Ar at 200 °C and 10 mTorr have resistivities of 1.8E-4 ohm-cm without the need for post deposition annealing. Average transmittance of the Ga-doped films is 93% over the visible and near infrared (IR) spectral regions, but free carrier absorption is a limiting factor further into the IR. After annealing in FG at 500 °C, a 300 nm Ar film has a Haacke figure of merit of 6.61E-2 sq. ohm. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

Abstract In this thesis work, crystal and phase structure, chemical composition and gas sensing properties of pulsed laser deposited vanadium oxide thin films were studied. Pulsed laser deposition was used to manufacture vanadium oxide thin films with various crystal structures, film morphologies and phase compositions. Both the well-known vanadium pentoxide V2O5, and a totally new stable phase in a solid-state thin-film form, V7O16, was produced. The existence of these phases was proven by several different characterization methods such as, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. The resistive gas sensing measurements of the films with pure V2O5 composition, and mixed phase compositions of V2O5 and V7O16, showed that behaviour of the electrical response to different gases at various measurement temperatures was dependent on the phase composition of the thin films. It was proved that in certain conditions the mixed phase films show p-type semiconducting gas sensing behaviour, instead of the pure n-type behaviour of V2O5. Both types of film compositions were shown to be highly sensitive to ammonia gas, down to 40 ppb-level. The mixed phase composition showed a higher response to ammonia compared to the pure V2O5 phase; however the pure V2O5 showed better long-term stability. Both sensing layer types also showed high selectivity to ammonia in comparison to NO and CO gases. Nanostructured pure V2O5 layers were successfully deposited on commercial microheater platforms and then used as a gas sensor. The V2O5 nanostructures were proven to be very promising candidates as gas sensor material to control the Selective Catalytic Reduction process used in the reduction of NOx gas emissions. The surface valence states of the thin film structures with various phase compositions were studied spectroscopically, and a clear connection between the valence states of the film surfaces and gas sensing properties was found. It was concluded that the pure V2O5 films also had some V4+ ions in the surface, and in the mixed phase thin films, the amount V4+ ions was already quite high, indicating a higher amount of oxygen vacancies in the thin film surface – another proof of the existence of V7O16 phase in the film composition. It is also suggested that the particular quantity of oxygen vacancies is one of the reasons for the high gas-sensing response of the thin films. / Tiivistelmä Tässä työssä tutkittiin pulssilaserkasvatettujen vanadiinioksidiohutkalvojen kide- ja faasirakenteita sekä ominaisuuksia kaasuantureina. Vanadiinioksidiohutkalvoja, jotka omaavat erilaiset kide- ja faasirakenteet, sekä erilaiset morfologiat valmistettiin pulssilaserkasvatuksella. Tunnetun V2O5 -faasin lisäksi myös V7O16 -faasi onnistuttiin valmistamaan ensimmäistä kertaa kiinteän aineen epäorgaanisena faasina ohutkalvorakenteeseen. Näiden erilaisten faasirakenteiden olemassaolo todistettiin käyttämällä useita menetelmiä kuten röntgendiffraktiota, Raman spektroskopiaa ja röntgenfotoelektronispektroskopiaa. Sekä ainoastaan V2O5 -faasia sisältäviä ohutkalvoja, että V2O5 ja V7O16 sekafaasirakenteen omaavia ohutkalvoja tutkittiin kaasuanturina, ja mittaustulokset osoittivat erilaisten kalvojen sähköisten kaasuanturivasteiden ominaisuuksien voimakkaan riippuvuuden kalvojen faasirakenteesta. Havaittiin myös, että sekafaasirakenne omaa tietyissä olosuhteissa p-tyyppisen puolijohteen sähkönjohtavuusmekanismin, toisin kuin puhdas V2O5-rakenne, joka on täysin n-tyyppinen. Molemmat ohutkalvotyypit todennettiin olevan erityisen herkkiä ammoniakki (NH3) kaasulle, jopa 40 miljardisosatasolle. Kalvo, jossa oli sekafaasirakenne, omasi korkeamman sähköisen kaasuvasteen kuin puhtaasta V2O5 faasista koostuva ohutkalvo, joka taas toisaalta omasi paremman stabiiliuden pidemmällä aikavälillä. Molemmat kaasuanturimateriaalit havaittiin selektiiviseksi NH3 -kaasulle verrattuna NO- ja CO-kaasuihin. Puhdas V2O5 nanorakenne onnistuttiin myös kasvattamaan kaupalliselle anturialustalle, ja käyttämään menestyksekkäästi herkkänä NH3- kaasuanturina. Lisäksi puhtaan V2O5 nanorakenteen todennettiin olevan erittäin lupaava kaasuanturimateriaali hyödynnettäväksi NOx-kaasupäästöjen vähentämiseen käytettävän SCR-katalyysiprosessin (Selective Catalytic Reduction) ohjauksessa. Ohutkalvotyyppien pinnan sähköistä rakennetta tutkittiin röntgenspektroskopiamenetelmillä, ja selvä yhteys materiaalien pintojen valenssitilojen ja kaasuanturiominaisuuksien välillä havaittiin. Huomattiin, että myös puhdas V2O5 ohutkalvo omaa pinnallaan pienen määrän V4+ -ioneja, ja että ohutkalvossa, jossa on sekafaasirakenne, V4+ -ionien määrä on suuri, ollen yksi todiste lisää V7O16 faasin olemassaoloon kalvon rakenteessa. Tästä johtuva happivakanssien olemassaolo on yksi syy näiden ohutkalvojen korkeaan kaasuherkkyyteen.

With increasing focus on the ill health and environmental effects of lead there is a greater push to develop Pb-free devices and materials. To this extent, ecofriendly and earth abundant LiNbO3-type ZnSnO3, a derivative of the ABO3 perovskite structure, has a high theoretically predicted polarization making it an excellent choice as a suitable alternative to lead based material such as PZT. In this work we present a novel synthesis procedure for the growth of various ZnSnO3 nanostructures by combined physical/chemical processes. Various ZnSnO3 nanostructures of different dimensions were grown from a ZnO:Al template layer on a Si (100) substrate deposited by pulsed laser deposition followed by a strategic solvothermal process. The ferroelectric properties of each sample were explored and a remanent polarization as high as nearly 30 μC/cm2 was found in aligned nanowire arrayed films. An in-depth understanding of the structure-property relationship is key to the future development of this material and is the subject of future investigations.

The presented thesis explores the magnetoelectric (ME) coupling in multiferroic thin film multilayers of BaTiO3 (BTO) and BiFeO3 (BFO). Multiferroics possess more than one ferroic order parameter, in this case ferroelectricity and anti-ferromagnetism. Cross-coupling between these otherwise separate order parameters promises great advantages in the fields of multistate memory, spintronics and even medical applications. The first major challenge in this field of study is the rarity of multiferroics. Second, most known multiferroics, both intrinsic and extrinsic in nature, possess very low ME coupling coefficients. In previous studies conducted by our group, BTO-BFO multilayers deposited by pulsed laser deposition (PLD) showed a ME coupling coefficient αME enhanced by one order of magnitude, when compared to single-layers of the intrinsic multiferroic BFO. However, the mechanism of ME coupling in such heterostructures is poorly understood until now. In this thesis, we used a selection of structural, chemical, electrical and magnetic measurements to maximize the αME-coefficient and shed light on the origin of this enhanced ME effect. The comparison of BTO-BFO multilayers over single-layers revealed not only enhanced ME-coupling, but also reduced mosaicity, roughness and leakage current density in multilayers. Following a parametric sample optimization, we achieved an atomically smooth interface roughness and vast improvements in the ferroelectric properties by introducing a shadow mask in the PLD process. We measured the highest αME-value so far of 480 Vcm-1Oe-1 for a multilayer with a double-layer thickness of only 4.6 nm, two orders of magnitude larger than the coefficient of 4 Vcm-1Oe-1 measured for BFO single-layers. The αME-coefficient in these multilayers stands in an inverse correlation with the double-layer thickness ddl. The influence of oxygen pressure during growth and BTO-BFO ratio on αME was shown to be neglible in comparison to that of ddl. From the characteristic dependencies of αME on magnetic bias field, temperature and ddl, we concluded the existence of an interface-driven coupling mechanism in BTO-BFO multilayers.:1 Introduction 2 Theory of Multiferroic Magnetoelectrics 2.1 Primary Ferroic Properties 2.2 Magnetoelectric Coupling 3 Materials 3.1 The General Structure of Perovskites ABX3 3.2 Strontium Titanate SrTiO3 3.3 Barium Titanate BaTiO3 3.4 Bismuth Ferrite BiFeO3 3.5 Heterostructures Based on BiFeO3 4 Experimental Section 4.1 Thin Film Fabrication 4.2 X–Ray Diffraction 4.3 Microscopic Techniques 4.4 Chemical Analysis Techniques 4.5 Ferroelectric Characterization 4.6 Magnetic Property Measurements 4.7 Measurement of the Magnetoelectric Coupling Coefficient 5 BaTiO3–BiFeO3 Heterostructures 5.1 General Properties of Single-Layers and Multilayers of BTO and BFO 5.2 PLD–Growth of BaTiO3–BiFeO3 Multilayers 5.3 Manipulation of Multilayer Properties through Design 5.4 Effectiveness of Eclipse–PLD 5.5 Enhanced ME Effect in BaTiO3–BiFeO3 Multilayers 6 Summary and Outlook A Magnetoelectric Measurement Setup B Magnetic Background Measurements C Polarized Neutron Reflectometry Literature Own and Contributed Work Acknowledgement Erratum

This thesis deals with the deposition of epitaxial chalcogenide (Ge2Sb2Te5 (GST225), GeTe and Sb2Te3) thin films and superlattice (SL) arrangement based on GeTe-Sb2Te3 using pulsed laser deposition (PLD) technique on (111)-oriented Si substrates. The thin films are characterized using in-situ RHEED, XRD, SEM, AFM and TEM. The epitaxial trigonal GST225 films with out-of-plane c-plane orientation were grown in 2D growth mode. For the first group of the films (substrate-target distance (dts) of ~7.5 cm), the epitaxial window was observed from 200 °C to 300 °C. By varying laser frequency, deposition rate as high as 42 nm/ min can be achieved. The deposition with a slight reduction of dts to ~6 cm (second group) at moderate Ts of 220 °C results in the epitaxial films with heterogeneous vacancy structures (coexisting metastable phases. i.e. with random and ordered vacancies, and stable trigonal phase). Thermal annealing (at 220 °C) leads to a phase transformation towards a pure trigonal phase. The epitaxial Sb2Te3 films with out-of-plane (0001) oriented trigonal structure were grown at Ts from 140 to 280 °C in 2D growth mode. The optimum Ts in terms of deposition rate and film quality was determined to be 240 °C. The epitaxial growth of Sb2Te3 thin films is initiated by the self-organized formation of a Sb/Te single-atomic passivation layer on the Si surface. The growth of GeTe was initialized by the formation of an ultra-thin amorphous layer. The films were predominantly grown in the mix of 2D and 3D growth modes. The deposited films possesses trigonal structure out-of-plane (0001)-orientated on Si(111). By employing a 2D-bonded Sb2Te3 as a seeding layer on Si(111), the epitaxial window of GeTe can be extended especially towards the lower temperature regime, up to 145 °C. Additionally, the surface topography can be significantly improved, indicating that the films are grown in 2D growth mode on the buffered substrate. The epitaxial SLs can be grown starting at Ts = 140 °C. Each layer of the SLs, i.e. Sb2Te3 and GeTe layer, was grown in 2D growth mode. An intermixing of GeTe and Sb2Te3 layers occurred at a higher temperature deposition. Studies on local structure of 140 °C-deposited SL showed that the SL consists of Ge-rich Ge(x+y)Sb(2–y)Tez and Sb2Te3 units intercalated by Van der Waals gaps with the inhomogeneity of layer thickness across the SL. The obtained results demonstrate the feasibility of PLD for deposition of good quality epitaxial chalcogenide thin films and SL structure on Si(111).

High-quality lattice-matched LaNiO3/LaMnO3 superlattices with monolayer terrace structure have been grown on both (111)- and (001)-oriented SrTiO3 substrates by pulsed laser deposition. In contrast to the previously reported experiments, a magnetic exchange bias is observed that reproducibly occurs in both (111)- and (001)-oriented superlattices with the thin single layers of 5 and 7 unit cells, respectively. The exchange bias is theoretically explained by charge transfer-induced magnetic moments at Ni atoms. Furthermore, magnetization data at low temperature suggest two magnetic phases in the superlattices, with Néel temperature around 10 K. Electrical transport measurements reveal a metal-insulator transition with strong localization of electrons in the superlattices with the thin LaNiO3 layers of 4 unit cells, in which the electrical transport is dominated by two-dimensional variable range hopping.

The dielectric function of heteroepitaxial YBiO3 grown on a-Al2O3 single crystals via pulsed laser deposition is determined in the spectral range from 0.03 eV to 4.5 eV by a simultaneous modeling of the spectroscopic ellipsometry and optical transmission data of YBiO3 films of different thicknesses. The (111)-oriented YBiO3 films are nominally unstrained and crystallize in a defective fluorite-type structure with a Fm3⎯⎯m space group. From the calculated absorption spectrum, a direct electronic bandgap energy of 3.6(1) eV and the signature of an indirect electronic transition around 0.5 eV are obtained. These values provide necessary experimental feedback to previous conflicting electronic band structure calculations predicting either a topologically trivial or a non-trivial insulating ground state in YBiO3.

CdTe and ZnTe are common semiconductors, currently used in a wide variety of applications. Heterostructures, composed of two or more layered materials, create further potential for the use of these semiconductors in the development of new technologies. In this thesis, the epitaxial growth of CdTe/ZnTe thin films and heterostructures are studied with the intention of better understanding the mechanisms by which they grow and how their overall structure and properties may be modified. Single-layer, bilayer, and multilayer structures were grown by pulsed laser deposition on sapphire substrates. The resulting crystal structure, interface, and optical properties were characterized using X-ray diffraction, UV-Vis spectroscopy, atomic force microscopy, and electron microscopy and spectroscopy techniques. It was found that the growth conditions have a direct impact on the crystal quality of these materials, that can be understood in terms of the growth dynamics and film-substrate interactions. Domain formation was also found to vary between CdTe and ZnTe depositions, revealing important information about their growth. This work presents methods of consistently producing high quality CdTe and ZnTe thin films and bilayers, and insight into how this may be applied to the growth of multilayer films. / Thesis / Master of Science (MSc)

<p>  </p> <p>Integration of functional thin films on flexible substrates has piqued interests owing to the needs of flexible devices. Selecting a suitable flexible substrate is crucial for such integration. Recently, muscovite mica has been developed as a flexible platform for functional thin film epitaxy growth. Mica can be easily peeled off due to the weak van der Waals interaction between different layers of mica, along with other advantages including cheap, high elasticity and thermal stability, biocompatible, <em>etc</em>. On the other hand, vertically aligned nanocomposites (VANs) have been attractive because of their unique anisotropic structures, which can achieve physical property anisotropy, easy tunability, out-of-plane strain engineering as well as combined multifunctionality. However, limited work on the integration of nanocomposite thin films on mica with tunable physical properties has been reported due to growth challenges. </p> <p>In this dissertation, different ceramic-metal VAN systems integrated on mica substrates towards different functionalities using pulsed laser deposition (PLD) have been demonstrated. The first chapter is on the integration of BaTiO3-Au nanocomposite system on mica. Tunable optical properties have been achieved by controlling the geometries of the Au nanostructures between nanoparticles and nanopillars by varying the growth temperature. The laser energy was also found to play a role in terms of the Au pillar dimension. The second chapter is on the integration of BaZrO3-Co VAN system on mica towards flexible spintronics. Tunable, anisotropic ferromagnetic property has been realized by controlling the aspect ratio of the Co pillars. The third chapter is on integration of BaTiO3-Fe VAN system on mica towards multiferroics. Different buffer layers have been tried out to facilitate the growth of VAN structure. Room temperature ferroelectric and anisotropic ferromagnetic properties of the films have been confirmed. The last chapter is focused on multiphase nitride-metal nanocomposite design and integration, with films showing unique optical and magnetic properties. The reliability and stability of the physical properties of the films have been verified though bending tests. The growth mechanism and criteria of ceramic-metal nanocomposite on mica have also been discussed. These demonstrations all pave a new way towards the integration and design of multifunctional nanocomposites towards flexible nanodevices.</p>

Compound semiconductors are the foundation of many electronic and optoelectronic devices. As a result semiconductor epitaxy can be viewed as the first significant step in device engineering. Accurate and reliable characterization methods are needed to measure semiconductor properties including optical, electrical, vibrational and crystal structure. In this thesis, the epitaxy of ZnTe thin films on sapphire substrate by Pulsed Laser Deposition system at different growth temperatures is studied. The texture analysis is inspected by Two Dimensional X-Ray Diffraction. The lattice constant of the films and strain studies are investigated by High Resolution X-Ray Diffraction. UV-Vis spectroscopy is applied to find absorption edge in ZnTe thin film in order to estimate optical bandgap. These common characterization methods reveal the great effect of growth temperature on crystalline and optical properties of ZnTe thin films. In addition, Raman spectroscopy is used for the first time in the Preston's group to examine vibrational modes in ZnTe thin films. This new characterization method, which is the main focus of this thesis, uncovers some new features of ZnTe thin films not accessible through other techniques. In this thesis, optimum experimental conditions, instrumentation and data analysis of Raman observations in thin films are studied in detail. The final results are in good agreement with other characterization methods and they can justify crystalline and optical observations. These results demonstrate that Raman spectroscopy is a non-destructive characterization method applicable to thin film analysis. / Thesis / Master of Applied Science (MASc)