Magnetophotoresistance in Pr 1–x CaxMnO3 Thin Films

In this work, a colossal magnetoresistive (CMR) Pr1−xCaxMnO3 (PCMO) man- ganite thin films and polycrystalline samples were studied with the main focus on the properties of the insulator to metal Mott phase transition. The polycrystalline PCMO samples were fabricated with the solid state reaction method. The polycrystalline sam- ples were further processed into the epitaxial thin films with the pulsed laser deposition method (PLD). The structural and magnetic properties of the samples were systemat- ically investigated and the thin films samples were further investigated with magneto- transport measurement where the thin films response to illumination was also studied. After the successful synthesis of polycrystalline PCMO samples with varying x = between 0.0 - 0.5, the magnetic characterization of the samples showed rich magnetic properties having the signatures of the magnetic phase coexistence of antiferromag- netic (AFM) and ferromagnetic (FM) ordering and cluster glass behaviour. With the increased doping concentration from x = 0.3 to 0.5, the AFM charge-order (CO) phase started to form up being strongest on the sample x = 0.5. This AFM CO phase could be melted with the high external magnetic field at temperatures below Neel’s tempera- ture TN inducing an irreversible first order metamagnetic AFM to FM phase transition. The strength of the AFM CO phase decreased with decreasing Ca concentration and increasing temperature. The polycrystalline PCMO samples with Ca concentrations of 0.3 - 0.5, showing metamagnetic behaviour, were selected for the fabrication of the thin film samples. The films were grown using two different in situ oxygen treatment temperatures at 500 ◦C and 700 ◦C in the PLD system. The films with x = 0.4 and 0.5 showed weaker AFM CO phase with greatly reduced melting fields when compared to polycrystalline samples. Also, the robustness of the AFM CO phase was further decreased in thin films with the lower oxygen treatment temperature of 500 ◦C. The magneto-transport measurements made on the thin films showed that the melting of AFM CO phase was connected to CMR effect where the increasing magnetic field induced an insulator to metal phase transition, which reduces the resistivity of the film around nine orders of magnitude. The use of illumination during the magneto-transport measurements showed a vari- ety of intriguing phenomena including magnetophotoresistance. The illumination had a huge effect to the insulator to metal transition (IMT) reducing the transition magnetic field significantly. Moreover, by magnetically biasing the thin films with the constant external magnetic field, the IMT could be induced by switching on the illumination.

Thin films of Cu, In and Sb chalcogenides as photovoltaic absorbers

Many different photovoltaic technologies are being developed for large-scale solar energy conversion such as crystalline silicon solar cells, thin film solar cells based on a-Si:H, CIGS and CdTe. As the demand for photovoltaics rapidly increases, there is a pressing need for the identification of new visible light absorbing materials for thin-film solar cells. Nowadays there are a wide range of earth-abundant absorber materials that have been studied around the world by different research groups. The current thin film photovoltaic market is dominated by technologies based on the use of CdTe and CIGS, these solar cells have been made with laboratory efficiencies up to 19.6% and 20.8% respectively. However, the scarcity and high cost of In, Ga and Te can limit in the long-term the production in large scale of photovoltaic devices. On the other hand, quaternary CZTSSe which contain abundant and inexpensive elements like Cu, Zn, Sn, S and Se has been a potential candidate for PV technology having solar cell efficiency up to 12.6%, however, there are still some challenges that must be accomplished for this material. Therefore, it is evident the need to find the alternative inexpensive and earth abundant materials for thin film solar cells. One of these alternatives is copper antimony sulfide(CuSbS2) which contains abundant and non-toxic elements which has a direct optical band gap of 1.5 eV, the optimum value for an absorber material in solar cells, suggesting this material as one among the new photovoltaic materials. This thesis work focuses on the preparation and characterization of In6Se7, CuSbS2 and CuSb(S1-xSex)2 thin films for their application as absorber material in photovoltaic structures using two stage process by the combination of chemical bath deposition and thermal evaporation.

Evaluation of the Genotoxicity of Chitosan Nanoparticles for Use in Food Packaging Films

The use of nanoparticles in food packaging has been proposed on the basis that it could improve protection of foods by, for example, reducing permeation of gases, minimizing odor loss, and increasing mechanical strength and thermal stability. Consequently, the impacts of such nanoparticles on organisms and on the environment need to be investigated to ensure their safe use. In an earlier study, Moura and others (2008a) described the effect of addition of chitosan (CS) and poly(methacrylic acid) (PMAA) nanoparticles on the mechanical properties, water vapor, and oxygen permeability of hydroxypropyl methylcellulose films used in food packaging. Here, the genotoxicity of different polymeric CS/PMAA nanoparticles (size 60, 82, and 111 nm) was evaluated at different concentration levels, using the Allium cepa chromosome damage test as well as cytogenetic tests employing human lymphocyte cultures. Test substrates were exposed to solutions containing nanoparticles at polymer mass concentrations of 1.8, 18, and 180 mg/L. Results showed no evidence of DNA damage caused by the nanoparticles (no significant numerical or structural changes were observed), however the 82 and 111 nm nanoparticles reduced mitotic index values at the highest concentration tested (180 mg/L), indicating that the nanoparticles were toxic to the cells used at this concentration. In the case of the 60 nm CS/PMAA nanoparticles, no significant changes in the mitotic index were observed at the concentration levels tested, indicating that these particles were not toxic. The techniques used show promising potential for application in tests of nanoparticle safety envisaging the future use of these materials in food packaging.

NONLINEAR EFFECTS IN MAGNETIC GARNET FILMS AND NONRECIPROCAL OPTICAL BLOCH OSCILLATIONS IN WAVEGUIDE ARRAYS

This dissertation presents detailed experimental and theoretical investigations of nonlinear and nonreciprocal effects in magnetic garnet films. The dissertation thus comprises two major sections. The first section concentrates on the study of a new class of nonlinear magneto-optic thin film materials possessing strong higher order magnetic susceptibility for nonlinear optical applications. The focus was on enlarging the nonlinear performance of ferrite garnet films by strain generation and compositional gradients in the sputter-deposition growth of these films. Under this project several bismuth-substituted yttrium iron garnet (Bi,Y) 3 (Fe,Ga)5 O12(acronym as Bi:YIG) films have been sputter-deposited over gadolinium gallium garnet (Gd 3 Ga5 O12 ) substrates and characterized for their nonlinear optical response. One of the important findings of this work is that lattice mismatch strain drives the second harmonic (SH) signal in the Bi:YIG films, in agreement with theoretical predictions; whereas micro-strain was found not to correlate significantly with SH signal at the micro-strain levels present in these films. This study also elaborates on the role of the film's constitutive elements and their concentration gradients in nonlinear response of the films. Ultrahigh sensitivity delivered by second harmonic generation provides a new exciting tool for studying magnetized surfaces and buried interfaces, making this work important from both a fundamental and application point of view. The second part of the dissertation addresses an important technological need; namely the development of an on-chip optical isolator for use in photonic integrated circuits. It is based on two related novel effects, nonreciprocal and unidirectional optical Bloch oscillations (BOs), recently proposed and developed by Professor Miguel Levy and myself. This dissertation work has established a comprehensive theoretical background for the implementation of these effects in magneto-optic waveguide arrays. The model systems we developed consist of photonic lattices in the form of one-dimensional waveguide arrays where an optical force is introduced into the array through geometrical design turning the beam sideways. Laterally displaced photons are periodically returned to a central guide by photonic crystal action. The effect leads to a novel oscillatory optical phenomenon that can be magnetically controlled and rendered unidirectional. An on-chip optical isolator was designed based on the unidirectionality of the magneto-opticBloch oscillatory motion. The proposed device delivers an isolation ratio as high as 36 dB that remains above 30 dB in a 0.7 nm wavelength bandwidth, at the telecommunication wavelength 1.55 μm. Slight modifications in isolator design allow one to achieve an even more impressive isolation ratio ~ 55 dB, but at the expense of smaller bandwidth. Moreover, the device allows multifunctionality, such as optical switching with a simultaneous isolation function, well suited for photonic integrated circuits.

Investigation of bonded hydrogen defects in nanocrystalline diamond films grown with nitrogen/methane/hydrogen plasma at high power conditions

In this work, we investigate the influence of some growth parameters such as high microwave power ranging from 3.0 to 4.0 kW and N2 additive on the incorporation of bonded hydrogen defects in nanocrystalline diamond (NCD) films grown through a small amount of pure N2 addition into conventional 4% CH4/H2 plasma using a 5 kW microwave plasma CVD system. Incorporation form and content of hydrogen point defects in the NCD films produced with pure N2 addition was analyzed by employing Fourier-transform infrared (FTIR) spectroscopy for the first time. A large amount of hydrogen related defects was detected in all the produced NCD films with N2 additive ranging from 29 to 87 µm thick with grain size from 47 nm to 31 nm. Furthermore, a specific new H related sharp absorption peak appears in all the NCD films grown with pure N2/CH4/H2 plasma at high powers and becomes stronger at powers higher than 3.0 kW and is even stronger than the 2920 cm−1 peak, which is commonly found in CVD diamond films. Based on these experimental findings, the role of high power and pure nitrogen addition on the growth of NCD films including hydrogen defect formation is analyzed and discussed.

Direct visualization of magnetic-field-induced magnetoelectric switching in multiferroic Aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High-resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm3), MR = 9.916 emu/g (81.5 emu/cm3), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14% compared with 4 to 7% for the CSD-grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.

Visualising In/Equalities through Contemporary Documentary Cinema. A Diffractive Reading of Feminist Practices in Spanish and Italian Non-Fiction Films

This thesis brings together feminist documentary film theory and feminist new materialism(s) to describe how feminist material-discursive practices in a sample of Spanish and Italian documentary cinema made between 2013-2018 (can) visualise gender in/equalities. The accomplished objectives have been: 1. Building a bridge between feminist documentary film theory and Karen Barad’s diffractive methodology by approaching non-fiction cinema that deals with social inequalities as a diffraction apparatus. 2. Developing a feminist toolbox for a response-able gaze by gathering different insights from feminist film theory. 3. Identifying feminist material-discursive practices in a sample of documentary films produced in Spain and Italy over the last six years (2013-2018). 4. Analysing the effects that these feminist material-discursive practices in documentary cinema have, particularly in terms of visualising gender in/equalities on both sides of the camera and on both sides of the screen. 5. Revealing patterns between the ten case studies by reading through one another (i.e. diffractively) insights raised in each one of them. In ten documentary films/case studies, I identify patterns of continuities and differences concerning feminist material-discursive practices at four levels: content, form, production and reception. In terms of contents, I detect two patterns in which feminist material-discursive practices may operate: enacting the right to appear or enacting the right to look back and/or against the grain. As for the forms, I exemplify how feminism politicises Bill Nichols’s six modes of representation. My analysis of production practices is elaborated along the filmmakers’ self-positions/situatedness, tensions/obstructions, and effects/affects/emotions regarding four key concepts: documentary cinema, equality, gender and feminism(s). And in the case of reception practices, I identify patterns of affective identification and/or intellectual reflections.

Thermodynamics of hydrogen absorption in Mg thin films and multilayers studied by electrochemical method

Electrochemical hydrogen loading is a technique used to produce and study the hydrogenation in metals starting from a liquid solution containing water. It is a possible alternative to another, well-established technique which loads hydrogen starting from its gas phase. In this work, the electrochemical method is used to understand the fundamental thermodynamics of hydrogen loading in constraint systems such as thin films on substrates, and possibly distinguish the role of interfaces, stresses and microstructure during the hydrogenation process. The systems under study are thin films of Pd, Mg/Pd, and Ti/Mg multilayers. Possible future technological applications may be in the field of hydrogen storage and hydrogen sensors. Towards the end, the experimental setup is modified by introducing an automatic relay. This change leads to improvements in the data analysis and in the attainable information on the kinetics of the systems.