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Dissertation
Multiferroic and magnetoelectric properties of Co-implanted ZnO thin films
Authors: ---
ISBN: 9789086497393 Year: 2014 Publisher: Leuven Katholieke Universiteit Leuven

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Abstract

The study of multiferroics and in particular the magnetoelectric couplin g is nowadays a new focus among the many hot topics in physics. The prom ising future of multiferroic materials lies in the coexistence of tradit ionally uncorrelated properties and the existence of a sizable coupling between them. Multiferroics provide a possibility to control one primary order by means of another primary order and create devices that are sui table for special conditions or can create multifunctionality. However, it is difficult to find multiferroicity due to the incompatiblity of fer romagnetism and ferroelectricity. The mechanism to establish magnetoelec tric coupling is always exotic and varying. Although there have been imp ortant research findings in multiferroics, such as lone-pair based multi ferroics, spin-driven ferroelectricity and multiferroic composites, etc, the field is far from mature yet, and the limitations lie both in the f abrication process as well as the complex measurement methods for charac terizing the magnetoelectrical properties. In this thesis, we achieved a structure consisting of Co atoms and Co na noparticles embedded in a crystalline ZnO thin film, aiming at finding m ultiferroicity and novel magnetotransport in such a nanocomposite system . We fabricated the system by pulsed laser deposition of ZnO followed by high-fluence Co ion implantation. The structural properties were charac terized by X-ray diffraction, transmission electron microscopy and X-ray absorption fine structure measurements. The majority of Co exists in th e matrix in an oxidized state (i.e. can be treated as a so-called (Zn,Co )O matrix). On the other hand, crystallized nanosize Co particles were f ound to be embedded in the (Zn,Co)O thin films, in which the thin film s till keeps good crystallinity. In such a complex nanocomposite system, t he electrical properties were studied by means of a helium-4 flow cryost at with a superconducting magnet down to 2.5 K. The low-temperature resi stance of the films followed the Efros-Shklovskii type variable-range-ho pping. Magnetoresistance revealed a spin-dependent signature that surviv es up to 250 K. Negative magnetoresistance exceeding 10% was observed at a magnetic field of 1 T. The magnetic properties were characterized by superconducting quantum interference device magnetometry. The composite reveals a characteristic superparamagnetic behavior, which is consistent with the presence of metallic Co nanoparticles. In addition, in some ca ses we observed exchange bias in the ZnO-Co system. This exchange bias e ffect constitutes, to the best of our knowledge, the first time observat ion of this effect in the ZnO-Co system. Temperature dependent dielectric constant measurements revealed relaxor ferroelectricity, which was further confirmed by polarization measuremen ts. The combination of the polarization measurement with a cryomagnetic system allowed us to determine the magnetoelectric coupling properties. A remarkable magnetoelectric coupling showed up when measuring the polar ization curve under an applied magnetic field. The unexpected relaxor fe rroelectricty is believed to be the result of the local lattice distorti on induced by the incorporation of the Co nanoparticles.


Dissertation
Ionic liquid technology in metal refining : dissolution of metal oxides and separation by solvent extraction
Authors: ---
ISBN: 9789086496884 Year: 2014 Publisher: Leuven Katholieke Universiteit Leuven

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Abstract

It goes without saying that point defects play a crucial role in semiconductors, either benificial or detrimental. Introduced as dopants, they ‘define’ one of the most typical electrical characteristics of semiconductors. But often, point defects - mostly intrinsic ones -may play a most detrimental role such as encountered at semiconductor/insulator interfaces where they may be at the origin of an untolerable amount of interface traps and/or recombination centers. As stated, it points to inadequate interface passivation. This makes the study of point defects an indispensible part of bulk semiconductor andsemiconductor/interface science. The current work fits within the latter prospect, where in a fundamental approach, the conventional electron spin resonance (ESR) technique is applied to attempt atomic identification of crucial device-impacting point defects. By means of multi-frequency ESR study, this work is concerned with point defects in ZnS:Mn nanowires, IIIV semiconductor GaAs/oxide entities, and (100)Si/oxide structures with oxides of low dielectric constant . In the first part, multi-frequency ESR and electron spectroscopy techniques were combined to study the symmetry and electronic structures of Mn2+ dopants in solvothermally synthesized c-ZnS nanowires (average diameter 5 nm and 10 nm) with mixed hexagonal and cubic stacking structures. Three different symmetry sites for incorporation of Mn2+ in ZnS have been identified, i.e., substitutional, interstitial/surface sites, and Mn clusters at the surface. Quantum confinement effects are observed, the data indicating a drastically higher efficiency of Mn2+ substitution in large diameter nanowires. The major part of this work has focused on the study of inherently generated interface defects during thermal oxidation of GaAs aiming to assess the atomic-structural identity. The study has been carried out on (100)GaAs/native oxide structures thermally grown in the range Tox = 350-615 oC on both powders and slices of semi-insulating (100)GaAs. Generally, four types of ESR signals (defects) are observed.The first major one is undubiously identified as the As antisite defect which upon oxidation is seen, from Tox = 350 °C onward to be generated in densities increasing with Tox reaching alarmingly high levels (~ 1013 cm-2). This compellingly reveals substantial generation of interfacial 75As+Ga antisites in registry with the GaAs substrate layer, thus providing solid independent evidence of substantial interfacial As enrichment, appearing as endemic to oxidation of GaAs, and at the same time providing an answerof how a major part of excess As gets interfacially incorporated. Given the known electrical deep double donor attribute of As+Ga, direct identification is thus established of a major system of detrimental interface traps, well fit to cause Fermi level pinning. As to technological relevance, it indicates thatoxidation of the GaAs substrate should be efficiently avoided, or if occurred, the impact of it should be strictly removed when aiming realization of device-grade semiconductor/insulator interfaces.A second spectrum, observed in oxidized c-GaAs slices after additional VUV irradiation, is composed of a quartet, centered at gc 2.268 for the applied field direction in the (100)GaAs sample plane, and shows distinct anisotropic behavior; this newly observed spectrum is suggested to concern a VGa in GaAs. Two more isotropic signals are observed at g 2.06 and 1.937. However, in absence of any attendant resolved hyperfine structure, no atomic model can be proposed. Finally, also observed is the spectrum from substitutional Fe3+ ions introduced as compensation dopants (deep acceptors) in the semi-insulating parent GaAs substrate, of which the inferred crystal field data are found to comply will with previous results. The next part of the work deals with the study of CZ-(100)Si/insulator structures with organosilicate films of low dielectric constant grown at 300 oC. This deals with the observation of the NL8 ESR spectrum of C2v symmetry defect −a thermal double donor, which is found to be introduced in the c-Si substrate during a short UV-assisted thermal curing treatment at 430 oC. A remarkable non-uniform (in depth) generation profile is observed which is concluded as being associated with interface stress. Theresults provide a different and affirmative illustration of the influence of in situ strain during the formation of thermal donors during thermal treatment. The result points to the presence of substantial interface stress.

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