Electrical transport properties of nanoparticle gold films made by the gas evaporation method were analysed using resistivity measurements. Low temperature electrical transport measurements showed a cross-over from a temperature range dominated by inelastic scattering to a temperature range dominated by elastic scattering, presumably by grain boundaries. This cross-over shifted towards lower temperatures with increasing grain size. High temperature in-situ electrical transport measurements were carried out in isothermal annealing experiments. Four types of samples, prepared at different deposition rates, were analysed. Samples prepared at low deposition rate displayed a higher thermal stability than samples prepared at high deposition rate. A relaxation model was fitted to the in-situ electrical transport data. The model included an activation energy, which was found to increase with increasing annealing temperature for all samples, thus pointing at the presence of pinning mechanisms in the samples. Optical properties of nanoparticle gold films were investigated in the 0.3 < λ < 12.5 µm wavelength range. A model taking grain boundary scattering into account was successfully fitted to the experimental data and it was shown that the infrared reflectance decreased with decreasing grain size as a consequence of increased grain boundary scattering. Nanoparticle tin-doped indium oxide films were made by spin-coating a dispersion containing the nanoparticles onto a substrate. The tin-doped indium oxide particles were prepared by a wet-chemical method. Optical properties were investigated in the 0.3 < λ < 30 µm wavelength range by reflectance and transmittance measurements. Effective medium theory was employed in the analyses of the optical data and information regarding film porosity and charge carrier concentration and mobility within the individual nanoparticles was obtained. It was found that ionized impurity scattering of the conduction electrons dominates within the particles. The temperature-dependent film resistivity was found to be governed by insulating barriers between clusters containing a large number of nanoparticles, thereby giving a negative temperature coefficient of resistivity.

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.

High strength-to-weight nanocrystalline alloy enabled conductor (NEC) prototypes were successfully developed by reinforcing an oxygen-free copper core material with electrodeposited cobalt phosphorus (CoP) coatings. A rule of mixtures approach was utilized to design the NEC prototypes to meet materials performance indices. Three unique NEC prototypes were produced with CoP coatings composed of alternating nanocrystalline (11 nm) and coarse-grained layers. The tensile properties were dependant on the coating microstructures, with tensile strengths of 1000 MPa, 970 MPa, and 900 MPa, respectively, and corresponding tensile elongations of 4.6%, 6.1%, and 10%, respectively. The electrical conductivity of the NEC prototypes was ~58 %IACS (resistivity of ~2.96 µΩ-cm). The rule of mixtures approach effectively predicted the tensile strength and conductivity. The NEC samples were significantly stronger than the incumbent high-strength aerospace conductor material, Be-Cu alloy CS95, which exhibits a tensile strength of only 655 MPa and conductivity of 63 %IACS.

Commercially available polycrystalline Ni (Ni200; grain size: 32 μm) and electrodeposited nanocrystalline Ni (grain size: 57 nm), Ni-2.6%Fe (grain size: 25 nm) and Ni-8.5%Fe (grain size: 20 nm) were analyzed for the phenomena of stress-induced heat generation and strain localization during plastic deformation at room temperature (i.e. 250C). Tensile specimens according to ASTM E8 standard dimensions were tested at strain rates of 10-2/s and 10-1/s, respectively, to record the amount of heat dissipated and the change of localized strain using a high resolution infrared (IR) detector and digital image correlation (DIC) camera, respectively. Results have shown that the maximum temperatures that were recorded in nanocrystalline Ni and Ni-Fe alloys were at least 300C lower than the onset temperatures for subgrain coalescence previously measured through differential scanning calorimetry. It can be concluded that thermally activated grain growth during tensile testing of nanocrystalline Ni and Ni-Fe alloys is not likely to occur.

Recent biosensors using glucose oxidase enzyme to detect glucose (“blood sugar”) were made with intrinsic conducting polymers such as poly pyrrole (PPY) to mediate the reaction. PPY coated electrodes were difficult to employ via eletropolymerization because PPY is only soluble in solvents potentially damaging to enzymes. Nano crystalline cellulose – poly pyrrole (NCC-PPY) colloid circumvents this by forming natural, enzyme compatible, and hydrophilic films mechanically bound to electrodes using easy-to-disperse colloids. NCC-PPY was studied as mediator to investigate use in biosensor applications. Using NCC-PPY film casted on microfabricated interdigitated electrodes, a glucose biosensor with sensitivity factor of 20 was achieved. NCC-PPY showed enhanced catalysis with no enzyme inactivation and a total current of 2mA. Enhanced sensitivity was attributed to resistance changes of doped PPY, redox mediation, and compatibility of cellulose with enzyme.

High strength-to-weight nanocrystalline alloy enabled conductor (NEC) prototypes were successfully developed by reinforcing an oxygen-free copper core material with electrodeposited cobalt phosphorus (CoP) coatings. A rule of mixtures approach was utilized to design the NEC prototypes to meet materials performance indices. Three unique NEC prototypes were produced with CoP coatings composed of alternating nanocrystalline (11 nm) and coarse-grained layers. The tensile properties were dependant on the coating microstructures, with tensile strengths of 1000 MPa, 970 MPa, and 900 MPa, respectively, and corresponding tensile elongations of 4.6%, 6.1%, and 10%, respectively. The electrical conductivity of the NEC prototypes was ~58 %IACS (resistivity of ~2.96 µΩ-cm). The rule of mixtures approach effectively predicted the tensile strength and conductivity. The NEC samples were significantly stronger than the incumbent high-strength aerospace conductor material, Be-Cu alloy CS95, which exhibits a tensile strength of only 655 MPa and conductivity of 63 %IACS.

Commercially available polycrystalline Ni (Ni200; grain size: 32 μm) and electrodeposited nanocrystalline Ni (grain size: 57 nm), Ni-2.6%Fe (grain size: 25 nm) and Ni-8.5%Fe (grain size: 20 nm) were analyzed for the phenomena of stress-induced heat generation and strain localization during plastic deformation at room temperature (i.e. 250C). Tensile specimens according to ASTM E8 standard dimensions were tested at strain rates of 10-2/s and 10-1/s, respectively, to record the amount of heat dissipated and the change of localized strain using a high resolution infrared (IR) detector and digital image correlation (DIC) camera, respectively. Results have shown that the maximum temperatures that were recorded in nanocrystalline Ni and Ni-Fe alloys were at least 300C lower than the onset temperatures for subgrain coalescence previously measured through differential scanning calorimetry. It can be concluded that thermally activated grain growth during tensile testing of nanocrystalline Ni and Ni-Fe alloys is not likely to occur.

Recent biosensors using glucose oxidase enzyme to detect glucose (“blood sugar”) were made with intrinsic conducting polymers such as poly pyrrole (PPY) to mediate the reaction. PPY coated electrodes were difficult to employ via eletropolymerization because PPY is only soluble in solvents potentially damaging to enzymes. Nano crystalline cellulose – poly pyrrole (NCC-PPY) colloid circumvents this by forming natural, enzyme compatible, and hydrophilic films mechanically bound to electrodes using easy-to-disperse colloids. NCC-PPY was studied as mediator to investigate use in biosensor applications. Using NCC-PPY film casted on microfabricated interdigitated electrodes, a glucose biosensor with sensitivity factor of 20 was achieved. NCC-PPY showed enhanced catalysis with no enzyme inactivation and a total current of 2mA. Enhanced sensitivity was attributed to resistance changes of doped PPY, redox mediation, and compatibility of cellulose with enzyme.

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.

Cette thèse est consacrée au silicium polymorphe hydrogéné (pm-Si:H). Elle porte tout d'abord sur une étude du pm-Si :H puis sur une étude des cellules photovoltaïques fabriquées à partir de ce matériau. Le pm-Si:H est formé de couches minces nanostructurées et peut être déposé par PECVD conventionnelle. Les effets des différents paramètres de dépôt (mélanges gazeux, pression, puissance RF, température du substrat) sur les propriétés du matériau ont été étudiés pour optimiser sa qualité. La caractérisation des couches a été un enjeu primordial. Pour cela, nous avons choisi de combiner une palette très large de méthodes de caractérisation (ellipsomètrie spectroscopique, exodiffusion d'hydrogène, SIMS, FTIR, AFM, etc...). A cause de la contribution des nanoparticules de silicium dans le plasma, la nature du dépôt du pm-Si:H montre la différence contrairement au a-Si:H pour lequel le dépôt se fait par le biais de radicaux ionisés. L'étude des conditions du procédé nous a conduit à fabriquer des cellules solaires d'un rendement initial de 9.22 % avec un facteur de forme élevé (74.1), mais aussi de démontrer des effets de vieillissement inhabituels, tels que i) une dégradation initiale rapide, ii) une dégradation irréversible, et iii) de grands changements structuraux macroscopiques. Nous avons découvert que le principal problème se situe entre le substrat et la couche mince de silicium. L'hydrogène moléculaire diffuse et s'accumule à l'interface entre le substrat et la couche mince, ce qui introduit un délaminage local qui a pour conséquence une dégradation initiale rapide des performances des cellules. Nous avons trouvé que sous éclairement une structure PIN facilite l'accumulation d'hydrogène et le délaminage à l'interface entre le substrat et la couche dopée p. Cependant, l'utilisation d'une structure NIP empêche l'accumulation d'hydrogène et le délaminage. Cela nous a permis de fabriquer des cellules solaires pm-Si:H de structure NIP d'un rendement stable de 8.43 %, mais aussi de démontrer une degradation minimale (10 %) après un vieillissement de 500 heures.