Combustion chemical vapor deposition (combustion CVD) is a thin film deposition process that uses a flame created by the ignition of an aerosol containing precursors dissolved in a flammable solvent. Combustion CVD is a relatively new technique for creating thin film oxide coatings. Combustion CVD has been successfully used to deposit high quality thin oxide films for potential applications such as thermal barrier coatings, dielectric thin films, composite interlayer coatings, etc. The present work involved developing the optimum parameters for deposition of thin films of yttria-stabilized zirconia (YSZ), alumina (Al₂O₃), and YSZ-alumina composites followed by a determination of the mechanical properties of the films (measured using nanoindentation) as a function of composition. The optimized parameters for deposition of YSZ, alumina, and YSZ-alumina composites onto single crystal a-plane alumina involved using an organic liquid as the flammable solvent and Y 2-ethylhexanoate, Zr 2-ethylhexanoate and Al acetylacetonate as the metal precursors at a 0.002 M concentration delivered at 4 ml/min at flame temperatures of 155 ℃ and substrate temperatures of 105 ℃. The resulting films were grown with deposition rates of ~ 1.5 μm/hr. Measurement of the mechanical properties (hardness, elastic modulus and fracture toughness) of the films was performed using a mechanical properties microprobe called the Nanoindenter®. In order to obtain valid results from nanoindentation, the combustion CVD films were optimized for minimum surface roughness and grown to a thickness of approximately 0.8 μm. With the penetration depth of the indenter at approximately 150 nm, the 800 nm thickness of the film made influences of the substrate on the measurements negligible. The hardnesses and elastic moduli of the YSZ-alumina films did not vary with the composition of the film. The fracture toughness, however, did show a dependence on the composition. It was found that second phase particles of alumina grown into a YSZ matrix increased the fracture toughness of the films (on average, 1.76 MPa• m⁰.⁵ for 100% YSZ to 2.49 MPa• m⁰.⁵ for 70 mol% YSZ/30 mol% alumina). Similarly, second phase particles of YSZ grown into an alumina matrix also increased the fracture toughness (on average, 2.20 MPa• m⁰.⁵ for 100% alumina to 2.45 MPa• m⁰.⁵ for 37.2 mol% YSZ/62.8 mol% alumina). Modeling of the fracture toughness of the YSZ-alumina films was successfully achieved by using the following toughening mechanisms: crack deflection from the second phase particles, grain bridging around the particles, and residual stress from the CTE mismatch between the film and the substrate and between the second phase particles and the matrix of the film.

This thesis comprises detailed experimental and theoretical investigations of the transport properties of one-dimensional nanostructures. Most of the work is dedicated to the exploration of the fascinating effects occurring in single wall carbon nanotubes (SWCNT). These particular nanostructures gained an overwhelming interest in the past two decades due to its outstanding electronic and mechanical features. We have investigated the properties of a novel family of carbon nanostructures, named here as Y-shaped rings. The studies show that they present very interesting quantum interference effects. A high structural stability under tensile strain and elevated temperatures is observed. Within the semi-classical potential adopted, the critical strain values of structure rupture lie in the same range of their pristine SWCNT counterparts. This is directly verified by the first observations of these ring-like structures in a transmission electron microscopy. A merging process of asymmetric into symmetric rings is investigated in-situ under electron beam irradiation at high temperatures. The electronic properties of these systems are theoretically studied using Monte Carlo simulations and environment dependent tight-binding calculations. From our results, we address the possibility of double-slit like interference processes of counter-propagating electron waves in the ring-like structures. The nature of well defined, sharp peaks in the density of states are determined as the discrete eigenenergies of the central loop part. Furthermore, the formation and dispersion of standing waves inside the ring is shown to originate from the quantum-dot like confinement of each branch between the leads. The obtained dispersion relation is shown to be the same occurring in purely one-dimensional quantum dots of similar geometries. Furthermore, Fabry-Perot-like interferences are observed. We established at the IFW a bottom-up processing route to fabricate nanotube based electronic devices. The SWCNTs are grown by chemical vapor deposition and we present a detailed study of the different approaches to obtain individual nanotubes suitable for a successful integration into electronic devices. Wet-chemistry and ultra-thin films as well as ferritin were employed as catalyst particles in the growth of SWCNT samples. By adjusting the optimized process parameters, we can control the obtained yield from thick nanotube forests down to just a couple of free-standing individual SWCNTs. The nanotubes are localized, contacted by standard e-beam lithography and characterized at ambient- as well as liquid helium temperatures. We usually obtain quite transparent contacts and the devices exhibit metallic or a mixed metallic/semiconducting behavior. The well-known memory effect upon gate voltage sweeping as well as single electron tunneling in the Coulomb blockade regime are addressed.

Eine Reihe wichtiger Wachstums- und Integrationsaspekte von Kohlenstoff-Nanoröhren wurde im Rahmen dieser Arbeit untersucht. Der Schwerpunkt der experimentellen Arbeit lag dabei hauptsächlich bei einschaligen Kohlenstoffnanoröhren (SWCNT). Das große Potential dieser Nanoröhren für Transistor-Anwendungen wurde durch die Herstellung einer Vielzahl funktionierender Bauelemente aus diesen Kohlenstoffnanoröhren mittels relativ einfacher Herstellungsprozesse demonstriert. Ein fundiertes Verständnis für die Abhängigkeiten des Nanoröhrenwachstums von einer Vielzahl an Parametern wurde mit Hilfe mehrerer tausend Wachstumsexperimente gesammelt. Verschiedene Katalysatormetalle, Kohlenstoffquellen und Katalysatorunterlagen wurden detailliert untersucht. Ein Hauptaugenmerk wurde dabei auf eine Reduzierung der Wachstumstemperatur gerichtet. Die niedrige Wachstumstemperatur spielt eine große Rolle für eine möglichst hohe Kompatibilität mit konventionellen Herstellungsverfahren der Silizium-Halbleitertechnik. Ein einfaches phänomenologisches Wachstumsmodell wurde für die Synthese von Nanoröhren mittels katalytisch-chemischer Gasphasen-Abscheidung (CCVD) formuliert. Dieses Modell basiert hauptsächlich auf der Oberflächendiffusion von adsorbierten Kohlenstoffverbindungen entlang der Seitenwände der Nanoröhren sowie auf der Oberfläche der Katalysatorunterlage. Das Modell ist eine wichtige Ergänzung zu dem VLS-Mechanismus. Ein Wachstumsverfahren zur Herstellung von Nanoröhren für niedrigere Temperaturen bis zu 600 °C wurde entwickelt. Experimentell wurde nachgewiesen, dass der Durchmesser des Katalysatorteilchens fast ausschließlich bestimmt, wie viele Schalen eine wachsende Nanoröhre bei geeigneten Wachstumsbedingungen hat. Es wurde zum ersten Mal gezeigt, dass einschalige Kohlenstoffnanoröhren auf Metallelektroden wachsen werden können, insofern eine dünne Aluminiumschicht als Trennschicht verwendet wird. Dadurch können in-situ kontaktierte Nanoröhren einfach hergestellt werden, was deren elektrische Charakterisierung weitaus erleichtert. Mittels stromloser Abscheidung von Nickel oder Palladium aus einer Lösung konnte eine deutliche Verbesserung der Kontaktwiderstände der in-situ-kontaktierten Nanoröhren erreicht werden. Durch Einbettung von Nanoröhren in eine Tantaloxidschicht konnten Transistoren mit einem Dielektrikum mit hoher relativer Dielektrizitätskonstante hergestellt werden. Die Tantaloxidschicht wurde mit einem neu entwickelten Tauchprozess abgeschieden. Erstmalig wurden Transistoren basierend auf Kohlenstoffnanoröhren hergestellt, die relativ hohe Ströme (Milliampere) mit einer Modulation bis zu einem Faktor 500 schalten können. Diese Transistoren beruhen auf einer Parallelschaltung einer großen Anzahl an Nanoröhren. Mit Hilfe der hergestellten Transistoren konnten die Eigenschaften einer großen Zahl von Nanoröhren untersucht werden, wobei große Unterschiede in den elektronischen Eigenschaften von metallischen Nanoröhren, halbleitenden Nanoröhren und Nanoröhren mit einer kleinen Bandlücke beobachtet wurden. / A number of very important growth and integration aspects of carbon nanotubes have been investigated during the course of this thesis. The focus was mainly on single-walled carbon nanotubes. Their potential for transistor applications was demonstrated by the successful fabrication of a variety of devices using rather simple processes. A detailed understanding of the dependence of SWCNT growth on a variety of parameters was obtained as the result of several thousand growth experiments. Various catalyst materials, gaseous carbon sources, and catalyst supports have been investigated. Special attention was paid to a considerable reduction of the growth temperature. A simple phenomenological growth model could be derived for CCVD of SWCNTs taking into account a number of effects observed during the various growth experiments. The model presented is mainly based on the surface diffusion of carbon species along the sidewalls of the carbon nanotubes or on the catalyst support and is an addition to the vapor-liquid-solid (VLS) mechanism. Growth methods for the CCVD synthesis of SWCNTs were developed for temperatures as low as 600 °C. It has been found that the size of the catalyst particle alone determines whether a SWCNT, DWCNT, or MWCNT will nucleate from a specific particle under suitable growth conditions. It could be demonstrated for the first time that SWCNTs can be grown on a variety of conducting materials if the catalyst is separated from the electrode by a thin Al layer. In-situ contacted SWCNTs can be easily obtained that way, largely facilitating the electronic characterization of as-grown SWCNTs. A tremendous improvement of the contacts of in-situ contacted SWCNTs could be achieved by electroless deposition. SWCNT growth on appropriate electrodes allowed the encapsulation of the nanotubes by electroless deposition of Ni and Pd, yielding good and reliable contacts. SWCNT transistors with a high-k dielectric could be fabricated by encapsulation of the nanotube with a tantalum oxide layer. The tantalum oxide was deposited by a newly developed dip-coat process. High-current SWCNT transistors consisting of a large number of SWCNTs in parallel were demonstrated for the first time during this work. Finally, the properties of a large number of CCVD grown SWCNTs have been investigated by electronic transport measurement. Large differences in the electronic transport have been observed for metallic, small band gap semiconducting (SGS), and semiconducting SWCNTs with small diameters.

The main objective of the present thesis is to deepen the understanding of the mechanisms involved in catalytic growth of carbon nanotubes (CNT) and related processes, such as the catalytic hydrogenation, and to use this knowledge to optimize the experimental approaches in order to gain better control in the synthesis and modification of carbon nanomaterials. Controlled growth of the CNT is achieved using gas-phase prepared catalyst particles (Fe, Co) which serve as individual catalytic nucleation sites in a chemical vapor deposition (CVD) process. These studies highlight that the controlled preparation of catalyst particles is a crucial step in order to control the CNT morphology. The resultant CNT diameter and the CNT density are found to increase with increasing nanoparticle diameter and density, respectively. The number of walls of the CNT also increases with increasing primary catalyst size. The experimentally derived correlations between the particle diameter on one hand and the CNT diameter and the CNT number of walls on the other hand are attributed to an increase of the catalyst's volume-to-surface area ratio with increasing particle size. While the availability of carbon dissolved within the catalyst at the point of nucleation is determined by the catalyst volume, the amount of carbon required to form a cap depends on the surface area of the catalyst particle. Electron microscopy studies of the catalyst/substrate/carbon interfaces of CNT grown from Fe nanoparticles reveal that the CNT walls are anchored to the oxide substrate which contests the general argument that the CNT walls stem from atomic steps at the catalyst. It is argued that after nucleation, the substrate itself provides a catalytic functionality towards the stimulation of ongoing CNT growth, whereas the catalytic activity of the metal particle is more restricted to the nucleation process. Selective hard-magnetic functionalization of CNT tips has been achieved in a plasma-enhanced CVD process. Hard-magnetically terminated CNT, i.e. CNT with a FePt nanoparticle at each tip, are directly grown using FePt catalysts. Fe/Pt thin films with a strongly over-stoichiometric Fe content in the starting catalyst composition yield CNT with a significant number of particles in the hard-magnetic phase. Anisotropic etching of graphite through Co catalyst particles in hydrogen atmosphere at elevated temperatures (i.e. catalytic hydrogenation) is reported. Catalytic hydrogenation is a potential key engineering route for the fabrication of graphene nanoribbons with atomic precision. While in previous studies the etching of zigzag channels was preferred, the present investigations reveal preferential etching of armchair channels, which provides a means to tailor graphene nanostructures with specific edge termination. Further, detailed morphological and structural characterization of the Co particles provide insight into the hydrogenation mechanism which is still a matter of controversy.

<p>This thesis deals with the main aspects in chemical vapordeposition (CVD) of silicon (Si) and silicon-germanium (Si_1-xGe_x) films for high-speed bipolar transistors.<i>In situ</i>doping of polycrystalline silicon (poly-Si)using phosphine (PH₃) and disilane (Si₂H₆) in a low-pressure CVD reactor was investigated toestablish a poly-Si emitter fabrication process. The growthkinetics and P incorporation was studied for amorphous Si filmgrowth. Hydrogen (H) incorporated in the as-deposited films wasrelated to growth kinetics and the energy for H₂desorption was extracted. Film properties such asresistivity, mobility, carrier concentration and grain growthwere studied after crystallization using either furnaceannealing or rapid thermal annealing (RTA). In order tointegrate an epitaxial base, non-selective epitaxial growth(NSEG) of Si and SiGe in a lamp-heated single-waferreduced-pressure CVD reactor was examined. The growth kineticsfor Si epitaxy and poly-Si deposition showed a differentdependence on the deposition conditions i.e. temperature andpressure. The growth rate difference was mainly due to growthkinetics rather than wafer surface emissivity effects. However,it was observed that the growth rate for Si epitaxy and poly-Sideposition was varying during growth and the time-dependencewas attributed to wafer surface emissivity variations. A modelto describe the emissivity effects was established, taking intoconsideration kinetics and the reactor heating mechanisms suchas heat absorption, emission andconduction. Growth ratevariations in opening of different sizes (local loading) andfor different oxide surface coverage (global loading) wereinvestigated. No local loading effects were observed, whileglobal loading effects were attributed to chemical as well astemperature effects. Finally, misfit dislocations formed in theSiGe epitaxy during NSEG were found to originate from theinterface between the epitaxial and polycrystalline regions.The dislocations tended to propagate across the activearea.</p><p><b>Keywords:</b>chemical vapor deposition (CVD), bipolarjunction transistor (BJT), heterojunction bipolar transistor(HBT), silicon-germanium (SiGe), epitaxy, poly-Si emitter,<i>in situ</i>doping, non-selective epitaxy (NSEG), loadingeffect, emissivity effect</p>

<p>Heterojunction bipolar transistors (HBT) based on SiGeC havebeen investigated. Two high-frequency architectures have beendesigned, fabricated and characterized. Different collectordesigns were applied either by using selective epitaxial growthdoped with phosphorous or by non-selective epitaxial growthdoped with arsenic. Both designs have a non-selectivelydeposited SiGeC base doped with boron and a poly-crystallineemitter doped with phosphorous.</p><p>Selective epitaxial growth of the collector layer has beendeveloped by using a reduced pressure chemical vapor deposition(RPCVD) technique. The incorporation of phosphorous and defectformation during selective deposition of these layers has beenstudied. A major problem of phosphorous-doping during selectiveepitaxy is segregation. Different methods, e.g. chemical orthermal oxidation, are shown to efficiently remove thesegregated dopants. Chemical-mechanical polishing (CMP) hasalso been used as an alternative to solve this problem. The CMPstep was successfully integrated in the HBT process flow.</p><p>Epitaxial growth of Si1-x-yGexCy layers for base layerapplications in bipolar transistors has been investigated indetail. The optimization of the growth parameters has beenperformed in order to incorporate carbon substitutionally inthe SiGe matrix without increasing the defect density in theepitaxial layers.</p><p>The thermal stability of npn SiGe-based heterojunctionstructures has been investigated. The influence of thediffusion of dopants in SiGe or in adjacent layers on thethermal stability of the structure has also been discussed.</p><p>SiGeC-based transistors with both non-selectively depositedcollector and selectively grown collector have been fabricatedand electrically characterized. The fabricated transistorsexhibit electrostatic current gain values in the range of 1000-2000. The cut-off frequency and maximum oscillation frequencyvary from 40-80 GHz and 15-30 GHz, respectively, depending onthe lateral design. The leakage current was investigated usinga selectively deposited collector design and possible causesfor leakage has been discussed. Solutions for decreasing thejunction leakage are proposed.</p><p><b>Key words:</b>Silicon-Germanium-Carbon (SiGeC),Heterojunction bipolar transistor (HBT), chemical vapordeposition (CVD), selective epitaxy, non-selective epitaxy,collector design, high-frequency measurement, dopantsegregation, thermal stability.</p>

<p>In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)_x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (T_C~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)_x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)_x prepared with this method as compared to V(TCNE)_x prepared by hitherto used methods.</p>

Copper interconnect requires liner materials that function as a diffusion barrier, a seed layer for electroplating, and an adhesion promoting layer. Ruthenium has been considered as a promising liner material, however it has been reported that Ru itself is not an effective Cu diffusion barrier due to its microstructure, which is polycrystalline with columnar grains. The screening study of Ru precursors revealed that all Ru films were polycrystalline with columnar structure, and, due to its strong 3D growth mode, a conformal and ultrathin Ru film was difficult to form, especially on high aspect ratio features. The microstructure of Ru films can be modified by incorporating P. Amorphous Ru(P) films are formed by chemical vapor deposition at 575 K using a single source precursor, cis-RuH₂(P(CH₃)₃)₄, or dual sources, Ru₃(CO)₁₂ and P(CH₃)₃ or P(C6H5)₃ The films contain Ru and P, which are in zero-valent states, and C as an impurity. Phosphorus dominantly affects the film microstructure, and incorporating > 13% P resulted in amorphous Ru(P) films. Metastable Ru(P) remains amorphous after annealing at 675 K for 3 hr, and starts recrystallization at ~775 K. The density of states analysis of the amorphous Ru(P) alloy illustrates metallic character of the films, and hybridization between Ru 4d and P 3p orbitals, which contributes to stabilizing the amorphous structure. Co-dosing P(CH)₃ with Ru₃(CO)₁₂ improves film step coverage, and the most conformal Ru(P) film is obtained with cis-RuH2(P(CH₃)₃)₄; a fully continuous 5 nm Ru(P) film is formed within 1 µm deep, 8:1 aspect ratio trenches. First principles density functional theory calculations illustrate degraded Cu/Ru adhesion by the presence of P at the interface, however, due to the strong Ru-Cu bonds, amorphous Ru(P) forms a stronger interface with Cu than Ta and TaN do. Cu diffusion studies at 575 K suggests improved barrier property of amorphous Ru(P) films over polycrystalline PVD Ru.

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Research Doctorate - Doctor of Philosophy (PhD) / Helium has the highest ionization energy of any species and is as a consequence difficult to detect by conventional means. On the other hand, it is the ideal surface probe, having no net charge or spin, a low mass and a short de Broglie wavelength. Therefore, there exists a strong incentive to develop a microscopy technique based on helium atom scattering. The purpose of this thesis is to investigate in detail how an efficient helium detector might be developed using the phenomenon of field ionization, an ionization method that relies on quantum mechanical tunneling rather than the more conventional electron impact ionization techniques. In particular, the work focusses on the potential use of a novel nanomaterial, carbon nanotubes, as the source of the high electric fields required for field ionization detection. In Chapter 1 we review the history of field ionization research and the properties and synthesis methods for carbon nanotubes. Chapter 2 describes the experimental apparatus and procedures used for the present research, and Chapter 3 introduces the theoretical framework and background for field ionization. In Chapter 4, the prototypical field ionization system is considered from a detector viewpoint. The work demonstrates that existing theory is not sufficiently quantitative for describing a field ionization detector and therefore a semi-empirical theory is advanced for that purpose. Chapter 5 considers the problem of nanotube field enhancement in detail using computational methods, leading to a complete description of the maximum field enhancement of a nanotube array based on the four fundamental array parameters. Efforts to synthesize carbon nanotubes in the Newcastle plasma-enhanced chemical vapor deposition system are described in Chapter 6. Several procedures are developed for reproducible growth of nanotube films and the chemical vapor deposition system is characterized with single parameter studies. Chapter 7 presents the results of electron field emission and helium field ionization experiments carried out using the grown nanotube films. We demonstrate for the first time the field ionization of helium using a planar film of carbon nanotubes. Finally, we conclude the investigation of field ionization detection in Chapter 8 with a discussion on how such a detection method integrates into a helium microscope and in particular we detail the design and initial calculations for the planned Newcastle helium microscope.