Nanocrystalline materials have generated immense scientific interest, primarily due to observations of significantly enhanced strength and hardness resulting from Hall-Petch grain size strengthening into the nano-regime. Unfortunately, however, most previous studies have been unable to present material strength measurements using established tensile tests because the most commonly accepted tensile test protocols call for specimen geometries that exceeded the capabilities of most nanocrystalline material synthesis processes. This has led to the development of non-standard mechanical test methodologies for the evaluation of miniature specimens, and/or the persistent use of hardness indentation as a proxy for tensile testing. This study explored why such alternative approaches can be misleading and revealed how reliable tensile ductility measurements and material strength information from hardness indentation may be obtained. To do so, an electrodeposition-based synthesis method to produce artifact-reduced specimens large enough for testing in accordance with ASTM E8 was developed. A large number of 161 samples were produced, tested, and the resultant data evaluated using Weibull statistical analysis. It was found that the impact of electroforming process control on both the absolute value and variability of achievable tensile elongation was strong. Tensile necking was found to obey similar processing quality and geometrical dependencies as in conventional engineering metals. However, unlike conventional engineering metals, intrinsic ductility (as measured by maximum uniform plastic strain) was unexpectedly observed to be independent of microstructure over the grain size range 10-80nm. This indicated that the underlying physical processes of grain boundary-mediated damage development are strain-oriented phenomena that can be best defined by a critical plastic strain regardless of the strength of the material as a whole. It was further shown that the HV = 3•σUTS expression is a reliable predictor of the relationship between hardness and strength for electrodeposited nanocrystalline materials, provided the material is ductile enough to sustain tensile deformation until the onset of necking instability. The widely used relationship HV = 3•σY was found to be inapplicable to this class of materials owing to the fact that they do not deform in an “ideally plastic” manner and instead exhibit plastic deformation that is characteristic of strain hardening behaviour.

Nanocrystalline silicon (nc-Si:H) is an attractive material for fabrication of low temperature, large area electronic devices due to superior properties versus the traditional amorphous silicon (a-Si:H) and polycrystalline silicon (polySi). Nanocrystalline silicon possess higher carrier mobility and better stability than a-Si:H and better device uniformity and lower fabrication cost than polySi. This thesis looks at the application of nc-Si:H material in fabricating two different diodes used for rectification and light generation. Optimization of n-type nc-Si:H deposited via plasma enhanced vapor chemical deposition (PECVD) was achieved through adjusting the concentration ratio of phosphine (PH3) dopant source gas versus silane (SiH4). Optimizing for dark conductivity, n+ nc-Si:H material with dark conductivity of 25.3 S/cm was deposited using a [PH3]/[SiH4] ratio of 2%. Using the optimized n+ nc-Si:H film, a p-n junction diode utilizing an undoped and an n+ nc-Si:H layers was fabricated designed for rectification use. The diode achieved a current density of 1 A/cm2, an ON/OFF current ratio of 106 and a non-ideality factor of 1.9. When the 200*200µm2 nc-Si:H diodes were employed in a full-wave bridge rectifier, a 2.6 V direct current voltage could be generated from an input sine wave signal with amplitude 2 VRMS and frequency of 13.56 MHz, thus demonstrating the feasibility of using nc-Si:H to fabricate diodes for using on radio frequency identification (RFID) tags. Nanocrystalline silicon was also applied in fabrication of a light emitting diode (LED), by utilizing the nanocrystals embedded inside nc-Si:H, inside which recombination of carriers could result in radiative recombination. By limiting the deposition time of the nc-Si:H, 10 – 20 nm thick films of nc-Si:H were used to fabrication a p-i-n structure LED with average crystallite size between 7.5 nm to 13.7 nm corresponding to an theoretical emission wavelengths in the near infrared region of 875 nm to 963 nm. Unfortunately, light emission from the nc-Si:H LED were not detected using two different methods. Undetectable emission could have been due to a combination of low recombination efficiency due to carriers recombining in defects in the a-Si:H matrix and majority of current travelling completely through the nc-Si:H films without recombining. A study of the thin intrinsic nc-Si:H films used in the LED was carried out. The thin films were found to be highly defected, with large variation in current-voltage relationship measured and hysteresis observed in the IV characteristic. Annealing the nc-Si:H films were found to cause a drop in conductivity explained through hydrogen effusion from the nc-Si:H film during annealing. Passivation of defects was achieved through the use of hydrogen plasma which resulted in a lowering of activation energy measured in the film. Oxygen plasma was also trialed for passivating the nc-Si:H film but the effect was only a temporary increase in current conduction attributed to oxygen ions chemisorbing temporarily at the film surface.

Nanocrystalline silicon (nc-Si:H) is an attractive material for fabrication of low temperature, large area electronic devices due to superior properties versus the traditional amorphous silicon (a-Si:H) and polycrystalline silicon (polySi). Nanocrystalline silicon possess higher carrier mobility and better stability than a-Si:H and better device uniformity and lower fabrication cost than polySi. This thesis looks at the application of nc-Si:H material in fabricating two different diodes used for rectification and light generation. Optimization of n-type nc-Si:H deposited via plasma enhanced vapor chemical deposition (PECVD) was achieved through adjusting the concentration ratio of phosphine (PH3) dopant source gas versus silane (SiH4). Optimizing for dark conductivity, n+ nc-Si:H material with dark conductivity of 25.3 S/cm was deposited using a [PH3]/[SiH4] ratio of 2%. Using the optimized n+ nc-Si:H film, a p-n junction diode utilizing an undoped and an n+ nc-Si:H layers was fabricated designed for rectification use. The diode achieved a current density of 1 A/cm2, an ON/OFF current ratio of 106 and a non-ideality factor of 1.9. When the 200*200µm2 nc-Si:H diodes were employed in a full-wave bridge rectifier, a 2.6 V direct current voltage could be generated from an input sine wave signal with amplitude 2 VRMS and frequency of 13.56 MHz, thus demonstrating the feasibility of using nc-Si:H to fabricate diodes for using on radio frequency identification (RFID) tags. Nanocrystalline silicon was also applied in fabrication of a light emitting diode (LED), by utilizing the nanocrystals embedded inside nc-Si:H, inside which recombination of carriers could result in radiative recombination. By limiting the deposition time of the nc-Si:H, 10 – 20 nm thick films of nc-Si:H were used to fabrication a p-i-n structure LED with average crystallite size between 7.5 nm to 13.7 nm corresponding to an theoretical emission wavelengths in the near infrared region of 875 nm to 963 nm. Unfortunately, light emission from the nc-Si:H LED were not detected using two different methods. Undetectable emission could have been due to a combination of low recombination efficiency due to carriers recombining in defects in the a-Si:H matrix and majority of current travelling completely through the nc-Si:H films without recombining. A study of the thin intrinsic nc-Si:H films used in the LED was carried out. The thin films were found to be highly defected, with large variation in current-voltage relationship measured and hysteresis observed in the IV characteristic. Annealing the nc-Si:H films were found to cause a drop in conductivity explained through hydrogen effusion from the nc-Si:H film during annealing. Passivation of defects was achieved through the use of hydrogen plasma which resulted in a lowering of activation energy measured in the film. Oxygen plasma was also trialed for passivating the nc-Si:H film but the effect was only a temporary increase in current conduction attributed to oxygen ions chemisorbing temporarily at the film surface.

A series of experiments was carried out to compare the structural and electronic properties of intrinsic nanocrystalline silicon (nc-Si:H) thin films deposited via continuous wave (cw) and pulsed (p)-PECVD at 150°C substrate temperature. Working at this temperature allows for the easy transfer of film recipes from glass to plastic substrates in the future. During the p-PECVD process the pulsing frequency was varied from 0.2 to 50 kHz at 50% duty cycle. Approximately 15% drop in the deposition rate was observed for the samples fabricated in p-PECVD compared to cw-PECVD. The optimum crystallinity and photo (σph) and dark conductivity (σD) were observed at 5 kHz pulsing frequency, with ~10% rise in crystallinity and about twofold rise in the σph and σD compared to cw-PECVD. However, for both the cw and p-PECVD nc-Si:H films, the observed σph and σD were one to two orders and three orders of magnitude higher respectively than those reported in literature. The average activation energy (EA) of 0.16 ∓ 0.01 eV for nc-Si:H films deposited using p-PECVD confirmed the presence of impurities, which led to the observation of the unusually high conductivity values. It was considered that the films were contaminated by the impurity atoms after they were exposed to air. Following the thin film characterization procedure, the optimized nc-Si:H film recipes, from cw and p-PECVD, were used to fabricate the absorber layer of thin film solar cells. The cells were then characterized for J-V and External Quantum Efficiency (EQE) parameters. The cell active layer fabricated from p-PECVD demonstrated higher power conversion efficiency (η) and a maximum EQE of 1.7 ∓ 0.06 % and 54.3% respectively, compared to 1.00 ∓ 0.04 % and 48.6% respectively for cw-PECVD. However, the observed η and EQE of both the cells were lower than a reported nc-Si:H cell fabricated via p-PECVD with similar absorber layer thickness. This was due to the poor Short-circuit Current Density (Jsc), Open-circuit Voltage (Voc), and Fill Factor (FF) of the cw and p-PECVD cells respectively, compared to the reported cell. The low Jsc resulted from the poor photocarrier collection at longer and shorter wavelengths and high series resistance (Rseries). On the other hand, the low Voc stemmed from the low shunt resistance (Rsh). It was inferred that the decrease in the Rsh occurred due to the inadequate electrical isolation of the individual cells and the contact between the n – layer and the front TCO contact at the edge of the p-i-n deposition area. Additionally, the net effect of the high Rseries and the low Rsh led to a decrease in the FF of the cells.

Cellulose is one of the most abundant biopolymers found in nature. Cellulose based derivatives have a number of advantages including recyclability, reproducibility, biocompatibility, biodegradability, cost effectiveness and availability in a wide variety of forms. Due to the benefits of cellulose based systems, this research study was aimed at developing novel cellulosic nanoparticles with potential pharmaceutical and personal care applications. Two different cellulosic systems were evaluated, each with its own benefits and proposed applications. The first project involves the synthesis and characterization of polyampholyte nanoparticles composed of chitosan and carboxymethyl cellulose (CMC), a cellulosic ether. EDC carbodiimide chemistry and inverse microemulsion technique was used to produce crosslinked nanoparticles. Chitosan and carboxymethyl cellulose provide amine and carboxylic acid functionality to the nanoparticles thereby making them pH responsive. Chitosan and carboxymethyl cellulose also make the nanoparticles biodegradable and biocompatible, making them suitable candidates for pharmaceutical applications. The synthesis was then extended to chitosan and modified methyl cellulose microgel system. The prime reason for using methyl cellulose was to introduce thermo-responsive characteristics to the microgel system. Methyl cellulose was modified by carboxymethylation to introduce carboxylic acid functionality, and the chitosan-modified methyl cellulose microgel system was found to be pH as well as temperature responsive. Several techniques were used to characterize the two microgel systems, for e.g. potentiometric and conductometric titrations, dynamic light scattering and zeta potential measurements. FTIR along with potentiometric and conductometric titration was used to confirm the carboxymethylation of methyl cellulose. For both systems, polyampholytic behaviour was observed in a pH range of 4-9. The microgels showed swelling at low and high pH values and deswelling at isoelectric point (IEP). Zeta potential values confirmed the presence of positive charges on the microgel at low pH, negative charges at high pH and neutral charge at the IEP. For chitosan-modified methyl cellulose microgel system, temperature dependent behaviour was observed with dynamic light scattering. The second research project involved the study of binding interaction between nanocrystalline cellulose (NCC) and an oppositely charged surfactant tetradecyl trimethyl ammonium bromide (TTAB). NCC is a crystalline form of cellulose obtained from natural sources like wood, cotton or animal sources. These rodlike nanocrystals prepared by acid hydrolysis of native cellulose possess negatively charged surface. The interaction between negatively charged NCC and cationic TTAB surfactant was examined and it was observed that in the presence of TTAB, aqueous suspensions of NCC became unstable and phase separated. A study of this kind is imperative since NCC suspensions are proposed to be used in personal care applications (such as shampoos and conditioners) which also consist of surfactant formulations. Therefore, NCC suspensions would not be useful for applications that employ an oppositely charged surfactant. In order to prevent destabilization, poly (ethylene glycol) methacrylate (PEGMA) chains were grafted on the NCC surface to prevent the phase separation in presence of a cationic surfactant. Grafting was carried out using the free radical approach. The NCC-TTAB polymer surfactant interactions were studied via isothermal titration calorimetry (ITC), surface tensiometry, conductivity measurements, phase separation and zeta potential measurements. The major forces involve in these systems are electrostatic and hydrophobic interactions. ITC and surface tension results confirmed two kinds of interactions: (i) electrostatically driven NCC-TTAB complexes formed in the bulk and at the interface and (ii) hydrophobically driven TTAB micellization on the NCC rods. Conductivity and surface tension results confirmed that the critical micelle concentration of TTAB (CMCTTAB) shifted to higher values in the presence of NCC. Phase separation measurements allowed us to identify the formation of large aggregates or hydrophobic flocs depending on the TTAB concentration. Formation of NCC-TTAB complexes in aqueous solutions was confirmed by a charge reversal from negative to positive charge on the NCC rods. The effect of electrolyte in shielding the negative charges on the NCC was observed from ITC, surface tensiometry and phase separation experiments. Several mechanisms have been proposed to explain the above results. Grafting of PEGMA on the NCC surface was confirmed using FTIR and ITC experiments. In phase separation experiments NCC-g-PEGMA samples showed greater stability in the presence of TTAB compared to unmodified NCC. By comparing ITC and phase separation results, an optimum grafting ratio (PEGMA : NCC) for steric stabilization was also proposed.

Nanomechanics emerged as chemists and physicists began fabricating nanoscale objects. However, there are some materials that have neither been fabricated nor mechanical investigated at the nanoscale, such as rhodium. Rhodium is used in many applications, especially in coatings and catalysis. To contribute to the understanding the nano-properties of this important material, rhodium was fabricated and mechanically investigated at the nanoscale. The nanopillars approach was employed to study size effects on mechanical properties. Nanopillars with different diameters were fabricated using electroplating followed by uniaxial compression tests. SEM was used as a quality control technique by imaging the pillars before and after compression to assure the absence of buckling, barrelling, or any other problems. Transmission electron microscopy (TEM) and SEM were used as microstructural characterization techniques, and the energy-dispersive X-ray spectroscopy (EDX) was used as the chemical characterization technique. Due to substrate induced effects, only the plastic region of the stress-strain curves were investigated, and it was revealed that rhodium softens with decreased nanopillar diameter. This softening/weakening effect was due to the nanocrystallinity of the fabricated pillars. This effect is consistent with the literature that demonstrates the reversed size effect of nanocrystalline metals, i.e., smaller is weaker. Further studies should focus on eliminating the substrate effect that was due to the adhesion layers between Rh and the silicon substrate being softer than Rh, consequently, causing Rh to sink into the adhesion layer when compressed and thus perturbing the stress-strain curve. Moreover, further investigation of other properties of Rh is required to achieve a comprehensive understanding of Rh at the nanoscale, and to render it suitable for specific, multivariable applications.

Chemical vapor deposition (CVD) has been the main method for synthesizing diamond thin films on hetero substrate materials since 1980s. It has been well acknowledged that both nucleation and growth of diamond on non-diamond surfaces without pre-treatment are very difficult and slow. Furthermore, the weak adhesion between the diamond thin films and substrates has been a major problem for widespread application of diamond thin films. Up to now, Si has been the most frequently used substrate for the study of diamond thin films and various methods, including bias and diamond powder scratching, have been applied to enhance diamond nucleation density. In the present study, nucleation and growth of diamond thin films on Ti3SiC2, a newly developed ceramic-metallic material, using Microwave Plasma Enhanced (MPE) and Hot-Filament (HF) CVD reactors were carried out. In addition, synchrotron-based Near Edge Extended X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) was used to identify the electronic and chemical structures of various NCD films. The results from MPECVD showed that a much higher diamond nucleation density and a much higher film growth rate can be obtained on Ti3SiC2 compared with on Si. Consequently, nanocrystalline diamond (NCD) thin films were feasibly synthesized on Ti3SiC2 under the typical conditions for microcrystalline diamond film synthesis. Furthermore, the diamond films on Ti3SiC2 exhibited better adhesion than on Si. The early stage growth of diamond thin films on Ti3SiC2 by HFCVD indicated that a nanowhisker-like diamond-graphite composite layer, different from diamond nucleation on Si, initially formed on the surface of Ti3SiC2, which resulted in high diamond nucleation density. These results indicate that Ti3SiC2 has great potentials to be used both as substrates and interlayers on metals for diamond thin film deposition and application. This research may greatly expand the tribological application of both Ti3SiC2 and diamond thin films. The results demonstrated that NEXAFS is a reliable and powerful tool to identify NCD films.

Im quaternären System Erdalkalimetall-Silicium-Chlor-Wasserstoff bildet sich bei der Umsetzung des Metalls mit einer SiCl4-H2-Atmosphäre eine quaternäre Phase. Diese metastabile Phase zerfällt beim Abkühlen in das Metallchlorid und Silicium in nanokristalliner Form. Die vorliegende Arbeit hat sich mit der tiefergehenden Charakterisierung der quaternären Phase beschäftigt. Dazu wurden die Eigenschaften des quaternären Systems aus den Eigenschaften der sechs binären und vier ternären Systemen abgeleitet. Die Oberfläche wurde erstmals mit Photoelektronenspektroskopie charakterisiert. Zusätzlich gelang erstmalig die Verfolgung der Bildungsreaktion durch Messung des Spannungsabfalls über das Reaktionssystem. Erste Ansätze zur Aufklärung des Bildungsmechanismus ausgehend von den Ergebnissen der Charakterisierung wurden zusätzlich aufgezeigt.

Nanocrystalline beta-silicon carbide (ß-SiC) was synthesized at relatively low temperature (<1300C) by carbothermal reduction (CTR) reaction in fine scale carbon/silica mixtures. The fine scale mixing of the reactants (i.e., carbon and silica) was achieved by solution-based processing and subsequent heat treatment. The mechanism of the CTR reaction in the current system was investigated from different aspects. The condensates of the volatile species generated during the CTR reaction was collected and analyzed. The results supported previous investigations which suggested that the CTR reaction is a multi-step process that involves silicon monoxide (SiO) vapor as a reaction intermediate. The kinetics of the CTR reaction was investigated by isothermal weight loss study and by the study which determined the amount of SiC formed via quantitative X- ray diffraction (QXRD) analysis. The results of kinetic study were consistent with the "shrinking-core" model, in which the reaction between SiO vapor and carbon at the carbon surface to produce SiC is the rate-controlling step. In addition, several techniques, including XRD, gas adsorption analysis, laser diffraction particle size analysis, SEM, TEM, etc., had been used to study the structural evolutions of the reaction product of CTR. It was demonstrated that the evolutions of product structure characteristics such as crystallite size, specific surface area, specific pore volume, pore size distribution, particle size distribution, and powder morphology, etc. were consistent with each other and provided support to the reaction mechanism proposed.

In the current research, a framework based on classical molecular dynamics (MD) is developed for computational mechanical analyses of complex nanoscale materials. The material system of focus is a combination of fcc-Al and and #945;-Fe₂O₃. The framework includes the development of an interatomic potential, a scalable parallel MD code, nanocrystalline composite structures, and methodologies for the quasistatic and dynamic strength analyses. The interatomic potential includes an embedded atom method (EAM) cluster functional, a Morse type pair function, and a second order electrostatic interaction function. The framework is applied to analyze the nanoscale mechanical behavior of the Al+Fe₂O₃ material system in two different settings. First, quasistatic strength analyses of nanocrystalline composites with average grain sizes varying from 3.9 nm to 7.2 nm are carried out. Second, shock wave propagation analyses are carried out in single crystalline Al, Fe₂O₃, and one of their interfaces. The quasistatic strength analyses reveal that the deformation mechanisms in the analyzed nanocrystalline structures are affected by a combination of factors including high fraction of grain boundary atoms and electrostatic forces. The slopes as well as the direct or inverse nature of observed Hall-Petch (H-P) relationships are strongly dependent upon the volume fraction of the Fe₂O₃ phase in the composites. The compressive strengths of single phase nanocrystalline structures are two to three times the tensile strengths owing to the differences in the movement of atoms in grain boundaries during compressive and tensile deformations. Analyses of shock wave propagation in single crystalline systems reveal that the shock wave velocity (US) and the particle velocity (UP) relationships as well as the type and the extent of shock-induced deformation in single crystals are strongly correlated with the choice of crystallographic orientation for the shock wave propagation. Analyses of shock wave propagation through an interface between Al and Fe2O3 point to a possible threshold UP value beyond which a shock-induced structural transformation that is reactive in nature in a region surrounding the interface may be taking place. Overall, the framework and the analyses establish an important computational approach for investigating the mechanical behavior of complex nanostructures at the atomic length- and time-scales.