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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Controlled Nucleation, Growth And Directed Assembly Of Nanocrystals With Engineered Interfaces For Applications

Kundu, Paromita 11 1900 (has links) (PDF)
Controlling the morphology of nanocrystals provides provides a possible pathway to tune properties and hence has been explored in depth. However, to obtain a wider spectrum of properties or for multi-functionality. Other strategies need to be devised. Combining different functional nanostructures to obtain a functional hybrid is one such strategy that holds promise for a wide range of applications. While this is simple in principle, there are no simple and general protocols for synthesis of such functional heterostructure. The challenge lies in producing a hybrid with good control over the structure and chemistry of the interfaces in the system. The use of molecular linkers or physical forces to form the hybrid has several drawbacks in terms of interface quality and stability. In this dissertation, a rational basis is developed for the evolution of symmetry forbidden FCC nanocrystals via wet chemical route which relies on appropriate choice of reagents and the reaction conditions for nucleation and growth. The concept is extended to devise general synthetic strategies for functional nanoheterostrcutres in solution via economic, facile and environment friendly routes. Electron microscopy and X-ray photoelectron spectroscopy has been used as the major tools for structural characterization of the materials and to investigates the reaction/formation mechanism. The properties of the synthesized materials are investigated primarily targeting the nanoelectronic and catalytic applications. The entire study reported in the thesis is organized as follow: chapter I leads to a general introduction of nanocrystals and role in different fields of application. It describes the motivation behind controlling the shape of nanocrystals and combining two or more nanostructures to obtain a functional heterostructure. The existing methodologies to achieve shape control and nanoscale hybrid/heterostructure with active interfaces are elaborated while indicating the role of morphology, interfaces and composition for enhanced activity/performance. The information on the chemical used for synthesis, routers adopted for synthesizing and the basic techniques utilized to characterize the materials in study are detailed in the respective chapters. Chapter 2 provides a study by which one can easily select an appropriate reductant for a metal couple to achieve the desired morphology. Moreover, the role of kinetics and the factors driving the kinetics in obtaining the symmetry breaking shapes like 2-D and I-D for Ag and Au nanocrystals is discussed in detail and validated by experiments. Chapter 3 describes the methodology to attach ultrafine Au nanowires to different nanosubstrates ranging from oxides to carbon (CNT/graphene) where the key step is heteronucleation of the Au (I) precursor on the substrate. Chapter 4 deals with the growth of ultrafine Au nanowires on various substrates and between pre-defined contacts to fabricate nanodevices. The mechanistic investigation directs to the controlled heterogeneous nucleation of the building units (Au nanoparticles) on substrate as the key step followed by its subsequent growth into wires in presence of Au nanoparticles in the medium. Kinetic control of the nucleation and growth step enabled precise control over the population and length of the wires. This is of immense importance for application like catalysis, sensors and nanoelectronics. Moreover, the method enabled the first time electrical transport studies on these wires which revealed an insulating behavior in such metallic wires on progressive lowering of temperature down to few kelvins. The concept of heterogeneous nucleation is extended to design nanoscale heterogeneous in the following three chapters where primarily a precursor coating is formed on a nanosubstrate, viz. ZnO nanorods and graphene, and converted to the phase of interest in a controlled manner to obtain the desired morphology. In each of the chapters the mechanisms of formation of the heterostructure are discussed in detail. Chapter 5 deals with formation of semiconductor based heterostructure like ZnO/CdS in solution by aqueous route. The material has been demonstrated as a potential visible light catalyst for dye degradation with enhanced activity. The interfacial chemistry could be tuned appropriately to achieve high activity in the catalyst by simple wet chemical route. In chapter 6, an ultrafast, facile, green route to obtain oxide supported metal catalyst has been demonstrated. ZnO/Au heterostructures were designed with well defined morphology and studied for low temperature CO oxidation reaction. Detail investigation reveals the surface doping of ZnO with Au the nucleation process leading to active ionic sites for CO oxidation. Chapter 7 demonstrate a rapid and economically viable route to graphene based pt catalysts where a synergistic co-reduction mechanism operates between the metal precursor and the graphic oxide to from the heterostructure. The obtained G-Pt heterostructure exhibits high catalytic activity for methanol oxidation reaction and hydrogen convention at ambient conditions. Finally a conclusion is drawn, highlighting the possibilities and prospects that the study leads to.
12

Probing Magnetic And Structural Properties Of Metallic Nanowires Using Resistivity Noise

Singh, Amrita 09 1900 (has links) (PDF)
The main focus of this thesis work has been the study of domain wall (DW) dynamics in disordered cylindrical nanomagnets. The study attempts to accurately quantify the stochasticity associated with driven (temperature/magnetic field/spin-torque) DW kinetics. Our results as summarized below, are particularly relevant with regard to the technological advancement of DW based magnetoelectronic devices. 1. Temperature dependent noise measurements showed an exponential increase in noise mag-nitude, which was explained in terms of thermally activated DW depinning within the Neel-Brown framework. The frequency-dependence of noise also indicated a crossover from nondiffusive kinetics to long-range diffusion of DWs at higher temperatures. We also observed strong collective depinning, which must be considered when implementing these nanowires in magnetoelectronic devices. 2. Our noise measurements were sensitive enough to detect not only the stochasticity in DW propagation (diffusive random walk) but also their nucleation in the presence of magnetic field down to a single DW unit inside an isolated single Ni nanowire. Controlled injection and detection of individual DWs is critical in designing DW based memory devices. 3. The spectral slope of noise was observed to be sensitive to DWkinetics that reveals a creep-like behavior of the DWs at the depinning threshold, and diffusive DW motion at higher spin torque drive. Different regimes of DW kinetics were characterized by universal kinetic exponents. Noise measurements also revealed that the critical current density and DW pinning energy can be significantly reduced in a magnetically coupled vertical ensemble of nanowires. This was attributed to strong dipolar interaction between the nanowires. Our results are particularly important in view of recent proposals for low power consumption magnetic storage devices that rely on DW motion. In all our experiments, the critical magnetic field/current density, required to set the DWs in duffusive kinetics, were found to be much smaller than the reported values for nanostrips. This could be attributed to the circular cross section of nanowires, where massless DWs results in the absence of Walker breakdown and hence in zero critical current density. At present the contribution from the non-adiabaticity, which acts as an effective field and can reduce the crit- ical current density, can not be denied. The main di±culty in quantifying the non-adiabatic spin-torque is that not only does it contain contributions due to non-adiabatic transport but also due to spin-relaxation provided by magnetic impurities or the sources for spin-orbit scattering. Fortunately, in cylindrical nanomagnet, non-adiabaticity does not affect the DW motion. There- fore, cylindrical NWs may be promising candidate for future magnetic storage devices. However, a systematic experimental study of DW dynamics in cylindrical nanomagnets is lacking. In chapter 7, silver nanowires (AgNWs) are shown to be stabilized in fcc or hcp crystal structure, depending on the electrochemical growth conditions. The AgNWs stabilized in hcp crystal structure are shown to exhibit exotic structural properties i.e. ultra low noise level, thermally driven unconventional structural phase transformation, and time dependent structural relaxation. Ultra noise level makes hcp AgNWs suitable for application in nanoelectronics and the structural transformation may be exploited for use in smart materials. Though time resolved transmission electron microscopy and noise measurements provide some understanding of the hcp AgNWs formation, the precise growth mechanism is still not clear. Future scope of the work The results in this thesis provide the groundwork for a good understanding of stochastic DW kinetics in isolated as well as ensemble of magnetic nanocylinders. Some extensions to this work that would help expand and strengthen the results, are listed below; 1. In all the nanocylinders used for our experiments the source of stochasticity in DWkinetics were randomly distributed structural defects. For a controlled injection and detection of DWs between the voltage probes, it would be of great importance to fabricate artificial notches (pinning centers) in the NW. These notches can be fabricated either by using nano-indentation or by a focussed ion beam. 2. To investigate whether DWs in different parts of the nanowire exhibit spatio-temporal correlation, a simultaneous detection of DWkinetics (through noise measurement) between different volage probes needs to be done. If the propagation time of DWs scales with the distance between the voltage probes, we can be confident of our velocity measurement. Then, by recording the DWvelocity as function of eld/current for nanowire (or nanostrip) absence (or presence) of the Walker breakdown can be probed. This would be a significant result for future spintronic devices. With an accurate determination of velocity even non- adiabaticity parameter may be calculated and one can see its effect on DW dynamics. 3. A complete understanding of sustained avalanches at finite magnetic fields, characterized by a high spectral exponent (a>¸ 2:5) in an ensemble of nanowires is still lacking. Per- forming a controlled experiment on a single nanowire, by varying the number of nanowires in the alumina matrix, one can study the chaotic dynamics of DWs in the ensemble in very accurate manner. All the experiments on AgNWs were performed on ensembles. The large change in a as well as noise magnitude in hcp AgNWs could arise from stress relaxation due to the presence of an insulating matrix or structural relaxation, determined by the nanowire growth kinetics. To resolve this issue, time and temperature dependent noise measurements should be performed on single nanowire stabilized in both hcp and fcc crystal structure.

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