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Title:Growth and applicability of radiation-responsive silica nanowires
Author(s):Bettge, Martin
Director of Research:Yu, Min-Feng
Doctoral Committee Chair(s):Yu, Min-Feng
Doctoral Committee Member(s):Rockett, Angus A.; Rogers, John A.; Ferreira, Placid M.
Department / Program:Mechanical Sci & Engineering
Discipline:Mechanical Engineering
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):silicon oxide
silica, nanowire
nanostructure
plasma, VLS, vapor-liquid-solid
magnetron
sputtering
plasma-enhanced
ion-beam
nanowire array
nanostructured surface
lithium
battery
batteries
bending
alignment
nanowire orientation
radiation sensitivity
ion irrradiation
ion bombardment
indium
gallium
surface energy
surface tension
line tension
line energy
Abstract:Surface energetics play an important role in processes on the nanoscale. Nanowire growth via vapor-liquid-solid (VLS) mechanism is no exception in this regard. Interfacial and line energies are found to impose some fundamental limits during three-phase nanowire growth and lead to formation of stranded nanowires with fascinating characteristics such as high responsiveness towards ion irradiation. By using two materials with a relatively low surface energy (indium and silicon oxide) this is experimentally and theoretically demonstrated in this doctoral thesis. The augmentation of VLS nanowire growth with ion bombardment enables fabrication of vertically aligned silica nanowires over large areas. Synthesis of their arrays begins with a thin indium film deposited on a Si or SiO2 surface. At temperatures below 200C, the indium film becomes a self-organized seed layer of molten droplets, receiving a flux of atomic silicon by DC magnetron sputtering. Simultaneous vigorous ion bombardment through substrate biasing aligns the growing nanowires vertically and expedites mixing of oxygen and silicon into the indium. The vertical growth rate can reach up to 1000 nm-min^−1 in an environment containing only argon and traces of water vapor. Silicon oxide precipitates from each indium seed in the form of multiple thin strands having diameters less than 9 nm and practically independent of droplet size. The strands form a single loose bundle, eventually consolidating to form one vertically aligned nanowire. These observations are in stark contrast to conventional VLS growth in which one liquid droplet precipitates a single solid nanowire and in which the precipitated wire diameter is directly proportional to the droplet diameter. The origin of these differences is revealed through a detailed force balance analysis, analogous to Young‘s relation, at the three-phase line. The liquid-solid interfacial energy of indium/silica is found to be the largest energy contribution at the three-phase line with 670-850 mJ-m^-2. Our analysis further reveals the existence of an additional force at this line that behaves as a negative line tension (or line energy). Its contribution is relatively small, but important for stable and small nanowire growth. The value of the line tension lies in the range of -0.1 to -1.0 nJ-m^-1. Spontaneous alignment of these stranded, free-standing wires toward a source of directional ion irradiation is proposed to be driven by local surface area minimization. An intuitive model for this is provided and experimentally verified through post-growth reorientation of nanowire patterns over a wide range of angles with standard focused ion beam instrumentation. Ion-induced orientation control and modification of nanowire arrays might prove to be a powerful method for nanoscale surface engineering, potentially leading to surfaces with well-organized anisotropic topographies. Another potential application of aligned silica nanowires as templates for highly textured electrodes in lithium-ion batteries is also discussed. As textured thin films are expected to provide better cycle life and enhanced charge transport, their electrochemical performance is compared to planar thin films of equal mass using two secondary materials (amorphous silicon and lithium manganese oxide). Both materials are applied directly onto the wire arrays by conventional deposition tools and galvanostatically cycled against metallic lithium. Textured silicon films, for use as negative materials, show improved capacity retention compared to planar thin films. Capacity fade is found to be relatively constant at about 0.8% per cycle over 30 cycles. Significant charge trapping occurred due to massive formation of a solid-electrolyte-interface. Electrochemical cycling and impedance spectroscopy further demonstrate that kinetic and electrochemical behavior of the electrode is qualitatively similar for planar and for highly textured silicon thin films. Textured films of lithium manganese oxide (LiMn2O4), for use as positive materials, retain their unique texture after 30 cycles, as verified by scanning and transmission electron microscopy. Some accelerated capacity fade is however observed and attributed to chemical dissolution of the oxide material. Frequency-dependent impedances of textured oxide films are lower than those for planar films. These findings suggest that thin film texturing can indeed enhance some of the material’s electrochemical performance characteristics and can be applied to a wide range of materials through use of appropriate nanostructured templates. In summary, this dissertation outlines physical and chemical factors leading to the formation of free-standing and uniquely stranded nanowires. It also provides an outlook on how ion-induced nanowire bending and alignment could be exploited. Key technological advantages of the developed process are refractory nanowire growth at low substrate temperatures and the ability to form radiation-responsive nanowire arrays without the use of lithography or templates.
Issue Date:2011-05-25
URI:http://hdl.handle.net/2142/24069
Rights Information:Copyright 2011 Martin Bettge
Date Available in IDEALS:2011-05-25
Date Deposited:2011-05


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