In this thesis, investigations into fabricating tin oxide hydrogen gas sensors from films assembled by the deposition of tin clusters are reported. The tin clusters were formed in a UHV compatible cluster apparatus by DC magnetron sputtering and inert gas aggregation. Through SEM imaging, it was found that the morphology of tin cluster assembled films deposited onto silicon nitride substrates was highly coalesced. The coalescence between the clusters was significantly reduced by reacting the clusters with nitrogen before they were deposited. This resulted in granular films with a grain size close to that of the deposited clusters. The coalesced and granular tin films were used to fabricate tin oxide conducti-metric gas sensors. This was done by depositing the tin films onto gold contacts and then oxidising them by baking them at 250°C for 24 hours. The sensors were tested using a purpose built gas test rig. It was found that the sensors with the granular film morphology were much more sensitive to 500 ppm, 1000 ppm, and 5000 ppm of hydrogen at 200°C in ambient air with zero humidity. This was attributed to the smaller grain size and the larger surface area of the granular films.

In this thesis, investigations into fabricating tin oxide hydrogen gas sensors from films assembled by the deposition of tin clusters are reported. The tin clusters were formed in a UHV compatible cluster apparatus by DC magnetron sputtering and inert gas aggregation. Through SEM imaging, it was found that the morphology of tin cluster assembled films deposited onto silicon nitride substrates was highly coalesced. The coalescence between the clusters was significantly reduced by reacting the clusters with nitrogen before they were deposited. This resulted in granular films with a grain size close to that of the deposited clusters. The coalesced and granular tin films were used to fabricate tin oxide conducti-metric gas sensors. This was done by depositing the tin films onto gold contacts and then oxidising them by baking them at 250°C for 24 hours. The sensors were tested using a purpose built gas test rig. It was found that the sensors with the granular film morphology were much more sensitive to 500 ppm, 1000 ppm, and 5000 ppm of hydrogen at 200°C in ambient air with zero humidity. This was attributed to the smaller grain size and the larger surface area of the granular films.

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The work presented in this dissertation has been focused on structure, stability, electronic properties, and chemical bonding of atomic clusters and solid-state compounds. The common thread was development of chemically intuitive models and theoretical methods capable of describing and interpreting bonding and hence, structures of these compounds. Understanding how interactions between atoms in sub-nano clusters and solid-state compounds of certain compositions determine their structures, physical properties, and reactivities is essential for rational design of new materials, catalysts, and molecular devices. A significant part of this work presents joint experimental and theoretical studies of doped boron clusters. Several projects on carbon- and aluminum-substituted boron clusters were aimed at establishing their structures, energetic and electronic properties, and understanding bonding interactions. The dissertation introduces a series of peculiar clusters containing transition metal atoms inside perfectly symmetrical boron rings. These clusters, featuring planar octa-, nona-, and decacoordinated transition metal atoms, were designed based on a simple chemical bonding model governing stabilities of such species. One of the most important parts of this dissertation deals with chemical bonding in the solid state. The Adaptive Natural Density Partitioning method previously developed by the Boldyrev group at Utah State University has proven very efficient for understanding chemical bonding in clusters and complex molecules. In this work, a periodic implementation of this method has been developed, yielding a new theoretical tool capable of interpretation of bonding in solid state in chemically intuitive terms of localized and multi-center bonds.

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In this thesis study, a new method for finding the optimum geometries of atomic nanoparticles has been developed by modifying the well known diffusion Monte Carlo method which is used for electronic structure calculations of quantum mechanical systems. This method has been applied to homonuclear and heteronuclear atomic clusters with the aim of both testing the method and studying various properties of atomic clusters such as radial distribution of atoms and coordination numbers. Obtained results have been compared with the results obtained by other methods such as classical Monte Carlo and molecular dynamics. It has been realized that this new method usually finds local minima when it is applied alone and some techniques to escape from local minima on the potential energy surface have been developed. It has been concluded that these techniques of escaping from local minima are key factors in the global optimization procedure.

Transistors are the fundamental components of computer processors. The dimensions of transistors used in microprocessors are decreasing every year and the challenge of maintaining this trend now requires nanoscale dimensions. A potential method of achieving nanoscale dimensions is using atomic clusters as building blocks. It is therefore desirable to investigate transistor-like behaviour in cluster devices. Traditionally, transistor devices are made from semiconducting materials. It was therefore proposed that gated behaviour would be observable in devices that are fabricated from germanium clusters. A germanium cluster source was designed and built. Field effects were successfully observed in films of germanium clusters. Immediately after deposition, the gate effect of germanium cluster films was insignificant. As the films slowly oxidized in vacuum, a decrease in the overall carrier concentration was observed which lead to an increase in the gate effect, with a maximum change in resistance observed of 12%. When films of germanium clusters were exposed to air, a resistance decrease was observed, attributed to water vapour adsorbing on the surface. The phenomenon was further investigated and the proposed resistance change mechanism involves water vapour creating surface defects which act as donors and cause the electron concentration in the film to increase. Films of germanium clusters were sensitive to hydrogen concentrations above 1% in air, with up to a factor of 25 decrease in resistance observed at room temperature for 5% hydrogen concentration. Thin films were found to be most sensitive. The higher sensitivity was attributed to the larger surface-to-volume ratio. The proposed mechanism for sensing is that defects are created on the surface of the film, which in turn act as donors which cause the electron concentration in the film to increase. Bismuth is a semimetal and gate effects have previously been observed in bismuth nanowires. Parallel bismuth nanowires of 300nm diameter were successfully deposited at a distance of 200nm apart allowing one of the wires to be used as a gate. The gate effects observed in bismuth cluster structures were weak and inconclusive, with a small gate effect (change in resistance of 0.1%) observed at 11K in some devices.

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The object of this thesis is the study of nanostructured thin films using inelastic fight scattering and elastic x-ray scattering techniques. Their use in combination with other techniques is a powerful tool for the investigation of nanostructured materials. X-ray, Raman and Brillouin characterisation of cluster-assembled carbon films, promising for applications in the field of catalysis, hydrogen storage and field emission, is here presented. X-ray reflectivity (XRR) provided a measure of the density. Raman spectroscopy showed that the local bonding in these amorphous films depends on the size distribution of the clusters and that it is possible to select the cluster size in order to grow films with tailored properties. Brillouin scattering provided a characterisation at the mesoscopic scale and an estimate of the elastic constants, revealing a very soft material. XRR was employed to study density, layering and roughness of a wide range of amorphous carbon films grown with different techniques. Some films possess an internal layering due to plasma instabilities in the deposition apparatus. By comparing XRR with Electron Energy Loss Spectroscopy, a unique value for the electron "effective mass" was deduced and a general relationship between sp(^3)-content and density was found. XRR and H effusion were used to determine the hydrogen content. A study of the size-dependent melting temperature in tin nanoparticle thin films was undertaken with a combined use of X-Ray Diffraction (XRD) and light scattering. A redshift in the position of a Rayleigh peak in the temperature-dependent Brillouin measurements was shown to be related to the melting of the nanoparticles and explained by an effective medium model. XRD also provided information on the low-level of stress in the particles. Low-frequency Raman scattering was used to study the behaviour of the acoustic modes of a single particle as a function of temperature.

No description available.