The precise determination of the type and concentration of gases is of increasing importance in numerous applications. Despite the diverse operating principles of today´s gas sensors, technological trends can be summarized with the keyword miniaturization, because of the resulting benefits such as integrability and energy efficiency. This work deals with the development and fabrication of novel nanowire based gas sensors, which in comparison to conventional devices have an advantageous combination of high sensitivity and selectivity with low power consumption and small size. On the basis of grown silicon nanowires, sensors based on the functional principle of classical Schottky barrier field effect transistors with abrupt metal-semiconductor contacts are fabricated. The sensing performance of the devices is investigated with respect to the detection of ammonia. Ammonia concentrations down to 170 ppb are measured with a sensor response of more than 160 % and a theoretical limit of detection of 20 ppb is determined. Selectivity investigations show that no cross sensitivity to most common solvents occurring in living spaces exists. Moisture influences on the device are studied and reveal that the sensor responds within seconds, making it potentially suitable as humidity sensor. Moreover, it is shown that a higher relative humidity and higher temperatures decrease the sensor sensitivity. In terms of possible applications, it is a great advantage that the maximum sensitivity is achieved at 25 °C. With respect to sensitivity and selectivity an enhancement is demonstrated compared to most nanosensors known from the literature. Hence, the technology offers the potential to complement conventional measurement systems in future sensor technology especially in portable applications. / Die präzise Bestimmung der Art und Konzentration von Gasen erlangt in zahlreichen Anwendungsgebieten zunehmend an Bedeutung. Trotz der vielfältigen Wirkprinzipien heutiger Gassensoren lassen sich die technologischen Trends mit dem Schlagwort Miniaturisierung zusammenfassen, da sich daraus entscheidende Vorteile wie Integrierbarkeit und Energieeffizienz ergeben. Diese Arbeit beschäftigt sich mit der Entwicklung und Herstellung neuartiger nanodrahtbasierter Gassensoren, welche im Vergleich zu klassischen Sensoren eine vorteilhafte Kombination von hoher Sensitivität und Selektivität bei geringem Stromverbrauch und geringer Größe aufweisen. Auf der Grundlage gewachsener Silizium-Nanodrähte werden Sensoren mit abrupten Metall-Halbleiter-Kontakten hergestellt, welche auf dem Funktionsprinzip klassischer Schottkybarrieren-Feldeffekttransistoren beruhen. Die Eignung der Sensoren wird in Bezug auf die Detektion von Ammoniak untersucht. Dabei kann eine minimale Ammoniakkonzentration von 170 ppb mit einer Signaländerung von mehr als 160 % gemessen werden, wobei die theoretische Nachweisgrenze mit 20 ppb ermittelt wird. Selektivitätsuntersuchungen zeigen, dass keine Querempfindlichkeit gegenüber den am häufigsten in Wohnräumen vorkommenden Lösungsmitteln besteht. Feuchtigkeitseinflüsse auf den Sensor werden untersucht und es wird nachgewiesen, dass der Sensor Ansprechzeiten im Sekundenbereich besitzt, was ihn zu einem potenziell geeigneten Feuchtigkeitssensor macht. Darüber hinaus wird gezeigt, dass eine höhere relative Luftfeuchtigkeit und höhere Umgebungstemperaturen die Sensorsensitivität verringern. In Bezug auf mögliche Einsatzgebiete stellt die maximale Empfindlichkeit bei 25 °C einen großen Vorteil da. Bezogen auf Sensitivität und Selektivität wird somit eine Verbesserung im Vergleich zu den meisten aus der Literatur bekannten Nanosensoren demonstriert. Damit bietet die Technologie das Potential, konventionelle Messsysteme in zukünftiger Sensorik vor allem in portablen Anwendungen zu ergänzen.

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This dissertation presents heretofore undiscovered properties of Silicon Nanowires (SiNWs) grown by electroless process and presents mathematical solutions to the special problems of the oxidation and diffusion of dopants for SiNWs. Also presented here is a mathematical description of morphology of oxidized SiNWs. This dissertation is comprised of several discussions relating to SiNWs growth, oxidation, morphology and doping. In here is presented work derived from a long-term study of SiNWs. Several important aspects of SiNWs were investigated and the results published in journals and conference papers. The recession of SiNWs was heretofore unreported by other research groups. In our investigations, this began as a question, "How far into the substrate does the etching process go when this method is used to make SiNWs?" Our investigations showed that recession did take place, was controllable and that a number of variables were responsible. The growth mechanism of SiNWs grown by electroless process is discussed at length. The relation of exposed area to volume of solution is shown, derived from experimentation. A relation of Silver used to Si removed is presented, derived from experimentation. The agglomeration of SiNWs grown by the electroless process is presented. The oxidation of SiNWs is a subject of interest to many groups, although most other groups work with SiNWs grown by the VLS process, which is more difficult, time-consuming and expensive to do. The oxidation of planar Silicon (Si) is still a subject of study, even today, after many years of working with and refining our formulae, because of the changing needs of this science and industry. SiNWs oxidation formulae are more complicated than those for planar Si, partly because of their morphology and partly because of their scale. While planar Si only iv presents one orientation for oxidation, SiNWs present a range of orientations, usually everything between and ( the orientation is usually not presented during oxidation). This complicates the post-oxidation morphology to the extent that, subsequent to oxidation, SiNWs are more rectangular than cylindrical in shape. After etching to remove an oxidation layer from the SiNWs, the rectangular shape shifts 90° in orientation. In traditional oxidation, the Deal-Grove formulae are used, but when the oxidation must take place in very small layers, such as with nanoscale devices, the Massoud formulae have to be used. However, even with Massoud, these formulae are not as good because of the morphology. Deal-Grove and Massoud formulae are intended for use with planar Si. We present some formulae that show the change in shape of SiNWs during oxidation, due to their morphology. The diffusion of dopants in SiNWs is a subject few research groups have taken up. Most of the groups who have, use SiNWs grown by the VLS method to make measurements and report findings. In order to measure the diffusion of dopants in SiNWs, a controllable diameter is needed. There are a number of ways to measure diffusion in SiNWs, but none of the ones used so far apply well to SiNWs grown by electroless process. Usually these groups present some mathematical formulae to predict diffusion in SiNWs, but these seem to lack mathematical rigor. Diffusion is a process that is best understood using Fick’s Laws, which are applied to the problem of SiNWs in this dissertation. Diffusion is a science with a long history, going back at least 150 years. There are many formulae that can be used in the most common diffusion processes, but the processes involved with the diffusion of dopants in SiNWs is more complex than the simple diffusion processes that are fairly well-understood. Diffusion doping of SiNWs is a multiphase process that is more complex, first because it is multiphase and second because the second step involves a v multiplicity of diffusing elements, plus oxidation, which brings on the problems of moving boundaries. In this dissertation, we present solutions to these problems, and the two-step diffusion process for SiNWs.

Flame synthesis is recognized as a much cheaper and higher throughput process for carbon nanotube/nanofiber (CNT/CNF) production compared to conventional catalytic processes like chemical vapor deposition (CVD). Nanostructured carbon materials, such as carbon nanotubes and nanofibers, exhibit superhydrophobic behavior over a range of pH values, including for corrosive liquids. Part of this research reports the development of a rapid on-demand process for the synthesis of superhydrophobic surfaces on silicon (Si) discs using an ethylene-air nonpremixed flame. Such superhydrophobic behavior, combined with increase in effective surface area due to carbon nanostructure (CNS) deposition and corresponding desirable size (nanoscale roughness) attract the growth and attachment of microbial colonies to these CNS-enhanced substrates. This has potentially high-impact application in microbial fuel cells (MiFCs) whereby stainless steel (SS) meshes coated with flame-deposited CNS are used as anodes and the electrons produced by attaching biofilms can generate electricity in a fuel cell. However, despite such and many other applications and promise of carbon nanotubes (CNTs), their production is generally based on empirical principles. There are only a few CNT formation models that predict the dependence of CNT growth on various synthesis parameters. Typically, these do not incorporate a detailed mechanistic consideration of the various processes that are involved during CNT synthesis. Herein, this need is addressed and a model is presented for catalytic CNT growth that integrates various interdependent physical and chemical mechanisms involved in CNT production. It is validated by comparing its predictions with experimental measurements for CVD synthesis of CNTs and a concise parametric study is presented. The results are extrapolated for flame synthesis that is recognized as a desirable cost-effective process for the bulk synthesis of CNTs, as already mentioned. The last part of this dissertation discusses an extension of the CNT growth model to silicon nanowire/nanowhisker (SiNW) synthesis. SiNWs are synthesized by a number of methods — catalysis by a metal (involving vapor-liquid-solid or VLS growth mode), molecular beam epitaxy, thermal evaporation and laser ablation to name a few. Our model pertains to metal-catalyzed VLS growth mode. / Ph. D.

Silicon nanowires, silicon nanorods, and magnetic nanocrystals have shown interesting size, shape, mechanical, electronic, and/or magnetic properties and many have proposed their use in exciting applications. However, before these materials can be applied, it is critical to fully understand their properties and how to synthesize them economically and reproducibly. Silicon nanowires were synthesized in high boiling point ambient pressure solvents using gold and bismuth nanocrystals seeds and trisilane as the silicon precursor. Reactions temperatures as low as 410°C were used to promote the solution-liquid-solid (SLS) growth of silicon nanowires. The silicon nanowires synthesis was optimized to produce 5 mg of silicon nanowires with average diameters of 30 nm and lengths exceeding 2 [mu]m by adjusting the silicon to gold ratio in the injection mixture and reaction temperature. Silicon nanorods were synthesized using a solution-based arrested-SLS growth approach where gold seeds, trisilane, and a dodecylamine were vital to the success. Dodecylamine was found to prevent gold seed coalescence at high temperatures -- creating small diameter rods -- and bond to the crystalline silicon surface -- preventing silicon nanorod aggregation. Furthermore, an etching strategy was developed using an emulsion of aqua regia and chloroform to remove the gold seeds from the silicon nanorods tip. A thin silicon shell surrounding the gold seed of the silicon nanorod was subsequently observed. Multifunctional colloidal core-shell nanoparticles of iron platinum or iron oxide encapsulated in fluorescent dye doped silica shells were also synthesized. The as-prepared magnetic nanocrystals are initially hydrophobic and were coated with a uniform silica shell using a microemulsion approach. These colloidal heterostructures have the potential to be used as dual-purpose tags, exhibiting a fluorescent signal that could be combined with enhanced magnetic resonance imaging contrast. Compositionally-ordered, single domain, antiferromagnetic L1₂ FePt₃ and ferromagnetic L1₀ FePt nanocrystals were synthesized by coating colloidally-grown Pt-rich or stoichiometricly equal Fe-Pt nanocrystals with thermally-stable SiO₂ and annealing at high temperature. Without the silica coating, the nanocrystals transform predominately into the L1₀ FePt phase due to interparticle diffusion of Fe and Pt atoms. Magnetization measurements of the L1₂ FePt₃ nanocrystals revealed two antiferromagnetic transitions near the bulk Neél temperatures of 100K and 160K. Combining L1₂ FePt₃ nanocrystals with L1₀ FePt nanocrystals was found to produce a constriction in field-dependent magnetization loops that has previously been observed near zero applied field in ensemble measurements of single domain silica-coated L1₀ FePt nanocrystals. Dipole interactions between FePt@SiO₂ nanoparticles with varying SiO₂ shell thickness was also explored. / text

Semiconductor nanotechnology is today a very well studied subject, and demonstrations of possible applications and concepts are abundant. However, well-controlled mass-fabrication on the nanoscale is still a great challenge, and the lack of nanofabrication methods that provide the combination of required fabrication precision and high throughput, limits the large-scale use of nanodevices. This work aims in resolving some of the issues related to nanostructure fabrication, and deals with development of nanofabrication processes, the use of size-reduction for reaching true nanoscale dimensions (20 nm or below), and finally the optical and electrical characterization to understand the physics of the more successful structures and devices in this work. Due to its widespread use in microelectronics, silicon was the material of choice throughout this work. Initially, a fabrication process based on electron beam lithography (EBL) was designed, allowing controlled fabrication of devices of dimensions down to 30 nm, although, generally, initial device dimensions were above 70 nm, allowing the flexible but low-throughput EBL, to be replaced by state-of-the-art optical lithography in the case of industrialization of the process. A few main processes were developed throughout the course of this work, which were capable of defining silicon nanopillar and nano-wall arrays from bulk silicon, and silicon nanowire devices from silicon-on-insulator (SOI) material. Secondly, size-reduction, as a means of providing access to few-nanometer dimensions not available by current lithography techniques was investigated. An additional goal of the size-reduction studies was to find self-limiting mechanisms in the process, that would limit the impact of variations in the size and other imperfections of the initial structures. Thermal oxidation was investigated mainly for self-limited size-reduction of silicon nanopillars, resulting in well-defined quantum dot arrays of few-nm dimensions. Electrochemical etching was employed to size-reduce both silicon nanopillars and silicon nanowires down into the 10-nm regime. This being a novel application, a more thorough study of electrochemical etching of low-dimensional and thin-layer structures was performed as well as development of a micro-electrochemical cell, enabling electrochemical etching of fabricated nanowire devices with improved control. Finally, the combination of nanofabrication and size-reduction resulted in two successful device structures: Sparse and spatially well-controlled single silicon quantum dot arrays, and electrically connected size-reduced silicon nanowires. The quantum dot arrays were investigated through photoluminescence spectroscopy demonstrating for the first time atomic-like photoemission from single silicon quantum dots. The silicon nanowire devices were electrically characterized. The current transport through the device was determined to be through inversion layer electrons with surface states of the nanowire surfaces greatly affecting the conductance of the nanowire. A model was also proposed, capable of relating physical and electrical properties of the nanowires, as well as demonstrating the considerable influence of charged surface states on the nanowire conductance. / QC 20101101

Narrow silicon nanowires host a rich set of physical phenomena. Understanding these phenomena will open new opportunities for applications of silicon nanowires in optoelectronic devices and adds more functionality to silicon especially in those realms that bulk silicon may not operate remarkably. Compatibility of silicon nanowires with the mainstream fabrication technology is also advantageous. The main theme of this thesis is finding the possibility of using silicon nanowires in light sources; laser and light emitting diodes. Using Tight Binding (TB) and ab-initio Density Functional Theory (DFT) methods it was shown that axial strain can induce significant changes in the effective mass, density of states and bandgap of silicon nanowires. Generality of the observed effects was proven by investigating nanowires of different crystallography, diameter and material (e.g. germanium nanowires). The observed direct to indirect bandgap conversion suggests that strain is able to modulate the light emission properties of silicon nanowires. To investigate this possibility, spontaneous emission time was formulated using perturbation theory including Longitudinal Optical (LO) and Acoustic (LA) phonons. It was observed that corresponding to bandgap conversion, the spontaneous emission time can be modulated by more than one order of magnitude. This emanates from bandgap conversion and symmetry change of wave function in response to strain. A mechanism for population inversion was proposed in the thesis which is based on the Ensemble Monte Carlo (EMC) study of carrier statistics in direct and indirect conduction sub bands. By calculating all possible electron-phonon scattering mechanisms which may deplete the already populated indirect subband, it was shown that at different temperatures and under different electric fields there is a factor of 10 difference between the population of indirect and direct sub bands. This suggests that population inversion can be achieved by biasing an already strained nanowire in its indirect bandgap state. The light emission is possible then by releasing or inverting the strain direction. A few ideas of implementing this experiment were proposed as a patent application. Furthermore the photo absorption of silicon nanowires was calculated using TB method and the role of diameter, optical anisotropy and strain were investigated on band-edge absorption.

This thesis describes experiments on quantum dots made by locally gating one-dimensional quantum wires. The first experiment studies a double quantum dot device formed in a Ge/Si core/shell nanowire. In addition to measuring transport through the double dot, we detect changes in the charge occupancy of the double dot by capacitively coupling it to a third quantum dot on a separate nanowire using a floating gate. We demonstrate tunable tunnel coupling of the double dot and quantify the strength of the tunneling using the charge sensor. The second set of experiments concerns carbon nanotube double quantum dots. In the first nanotube experiment, spin-dependent transport through the double dot is compared in two sets of devices. The first set is made with carbon containing the natural abundance of \(^{12}C\) (99%) and \(^{13}C\) (1%), the second set with the 99% \(^{13}C\) and 1% \(^{12}C\). In the devices with predominantly \(^{13}C\), we find evidence in spin-dependent transport of the interaction between the electron spins and the \(^{13}C\) nuclear spins that was much stronger than expected and not present in the \(^{12}C\) devices. In the second nanotube experiment, pulsed gate experiments are used to measure the timescales of spin relaxation and dephasing in a two-electron double quantum dot. The relaxation time is longest at zero magnetic field and goes through a minimum at higher field, consistent with the spin-orbit-modified electronic spectrum of carbon nanotubes. We measure a short dephasing time consistent with the anomalously strong electron-nuclear interaction inferred from the first nanotube experiment. / Physics

Narrow silicon nanowires host a rich set of physical phenomena. Understanding these phenomena will open new opportunities for applications of silicon nanowires in optoelectronic devices and adds more functionality to silicon especially in those realms that bulk silicon may not operate remarkably. Compatibility of silicon nanowires with the mainstream fabrication technology is also advantageous. The main theme of this thesis is finding the possibility of using silicon nanowires in light sources; laser and light emitting diodes. Using Tight Binding (TB) and ab-initio Density Functional Theory (DFT) methods it was shown that axial strain can induce significant changes in the effective mass, density of states and bandgap of silicon nanowires. Generality of the observed effects was proven by investigating nanowires of different crystallography, diameter and material (e.g. germanium nanowires). The observed direct to indirect bandgap conversion suggests that strain is able to modulate the light emission properties of silicon nanowires. To investigate this possibility, spontaneous emission time was formulated using perturbation theory including Longitudinal Optical (LO) and Acoustic (LA) phonons. It was observed that corresponding to bandgap conversion, the spontaneous emission time can be modulated by more than one order of magnitude. This emanates from bandgap conversion and symmetry change of wave function in response to strain. A mechanism for population inversion was proposed in the thesis which is based on the Ensemble Monte Carlo (EMC) study of carrier statistics in direct and indirect conduction sub bands. By calculating all possible electron-phonon scattering mechanisms which may deplete the already populated indirect subband, it was shown that at different temperatures and under different electric fields there is a factor of 10 difference between the population of indirect and direct sub bands. This suggests that population inversion can be achieved by biasing an already strained nanowire in its indirect bandgap state. The light emission is possible then by releasing or inverting the strain direction. A few ideas of implementing this experiment were proposed as a patent application. Furthermore the photo absorption of silicon nanowires was calculated using TB method and the role of diameter, optical anisotropy and strain were investigated on band-edge absorption.

Silicon and silicon-based materials have been investigated for the fabrication of electronic, optoelectronic, solar, and structural/mechanical devices. To enable the continuous use of silicon-based materials for next generation device applications, new and inexpensive ways of fabricating features of silicon, and silica-based materials are needed. This dissertation investigates: 1) novel techniques for the fabrication of silica and silicon nanofeatures with potential application in the electronics and optoelectronics industry; 2) new designs of photomodifiable material systems (resists) for maskless patterning of silica filled composites for structural/mechanical applications. Sub-micron and nano-scaled features were fabricated onto silicon and silicon oxide substrates using a technique combining block copolymers and laser interference ablation. The sacrificial block copolymers are loaded with metallic salt precursors and patterned with a UV laser to generate device-oriented nanofeatures. New photopolymerizable material systems (negative tone resists) were developed based on curcumin photosensitizer and an epoxy-acrylate, vinylether, and vinylether-acrylate silica¬-loaded material systems. The cationic and radical mechanisms employed by the monomeric systems under a high vapor pressure mercury lamp source were investigated with several materials characterization techniques.