Date of Award

Summer 8-2011

Degree Type

Dissertation-Restricted

Degree Name

Ph.D.

Degree Program

Chemistry

Department

Chemistry

Major Professor

Wiley, John B.

Second Advisor

Tarr, Matthew A.

Third Advisor

Malkinski, Leszek

Fourth Advisor

Sankaranarayanan, Anathakrishnan

Fifth Advisor

Poudeu, P. Ferdinand

Abstract

In this study, template-based methods are used for the fabrication of various nanostructures such as nandots, nanorods, nanowires, nanotubes, and core-shell structures. Porous alumina membranes were employed as templates and metal nanostructures were synthesized in the templates by electrodeposition. By using lithography techniques, controlled patterned nanostructures were also fabricated on alumina templates. The magnetic properties of the various metal nanostructures were investigated. The pore size, interpore distance, and pore geometry highly affect magnetic properties of nanostructures grown in the templates. Hexagonally ordered porous alumina templates can be fabricated by two-step anodization. The pore diameters and interpore distances were readily controlled by appropriately changing anodization conditions and pore widening time. Alumina templates with various pore geometries were also successfully synthesized by changing applied voltage, increasing and decreasing, during a third anodization step. To understand magnetic properties of nanostructures with different aspect rations in the form of nanodots, nanorods, or nanowires, Fe nanostructures were fabricated in the templates by controlling of electrodeposition times. The coercivity of nanostructures increased with increasing aspect ratio. The anisotropy of the arrays was governed by the shape anisotropy of the magnetic objects with different aspect ratios.

nanowires in mild-hard alumina and conventional alumina templates showed distinct differences in the squareness of hysteresis loops and coercivity both as a function of pore structure and magnetic component. Iron oxide nanotubes with a unique inner-surface were also fabricated by an electrodeposition method. β-FeOOH nanotubes were grown in alumina templates and transformed into hematite and magnetite structures during various heating processes. Hematite nanotubes are composed of small nanoparticles less than 20 nm diameters and the hysteresis loops and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, hysteresis loops show ferromagnetism with weak coercivity at room temperature while FC-ZFC curves exhibit the Verwey transition at 125 K. For the patterning of nanowires, lithography techniques including nanosphere lithography and e-beam lithography were used. Nanosphere lithography used self-assembled PS spheres as a mask creates holes between spheres and the size of the holes is determined by the size and geometry of ordered PS spheres on the templates. This method can grow patterned nanowires arrays and also produce unique cup-shaped nanostructures with sizes ranging from micrometer down to several nanometers. E-beam lithography was also combined with template-based electrodeposition. Of these two lithographic methods, this one is the most powerful in the fabrication of patterned nanostructures with high aspect ratios. Various features and the sizes of patterned structures can be readily controlled. By the directing the pore diameters and interpore distances of the alumina template, the size and number of patterned nanowires are also adjustable.

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The University of New Orleans and its agents retain the non-exclusive license to archive and make accessible this dissertation or thesis in whole or part in all forms of media, now or hereafter known. The author retains all other ownership rights to the copyright of the thesis or dissertation.

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