Epitaxial Ti3GeC2 thin films were deposited on 4 degrees off-cut 4H-SiC(0001) using magnetron sputtering from high purity Ti, C, and Ge targets. Scanning electron microscopy and helium ion microscopy show that the Ti3GeC2 films grow by lateral step-flow with {11 (2) over bar0} faceting on the SiC surface. Using elastic recoil detection analysis, atomic force microscopy, and X-Ray diffraction the films were found to be substoichiometric in Ge with the presence of small Ge particles at the surface of the film.

In the present study, gold/surfactant core/shell colloidal nanoparticles with a controlled morphology and chemical composition have been obtained via the so-called sacrificial anode technique, carried out in galvanostatic mode. As synthesized Au-NPs had an average core diameter comprised between 4 and 8 nm, as a function of the electrochemical process experimental conditions. The UV-Vis characterization of gold nanocolloids showed clear spectroscopic size effects, affecting both the position and width of the nanoparticle surface plasmon resonance peak. The nanomaterial surface spectroscopic characterization showed the presence of two chemical states, namely nanostructured Au(0) (its abundance being higher than 90%) and Au(I). Au-NPs were then deposited on the top of a capacitive field effect sensor and subjected to a mild thermal annealing aiming at removing the excess of stabilizing surfactant molecules. Au-NP sensors were tested towards some gases found in automotive gas exhausts. The sensing device showed the largest response towards NOx, and much smaller - if any - responses towards interferent species such as NH3, H-2, CO, and hydrocarbons.

The high-temperature stability of a Pt/TaSi2/Ni/SiC ohmic contact metallization scheme was characterized using a combination of current-voltage measurements, Auger electron spectroscopy, and transmission electron microscopy imaging and associated analytical techniques. Increasing the thicknesses of the Pt and TaSi2 layers promoted electrical stability of the contacts, which remained ohmic at 600A degrees C in air for the extent of heat treatment; the specific contact resistance showed only a gradual increase from an initial value of 5.2 x 10(-5) Omega cm(2). We observed a continuous silicon oxide layer in the thinner contact structures, which failed after 36 h of heating. Meanwhile, thicker contacts with enhanced stability contained a much lower oxygen concentration that was distributed across the contact layers, precluding the formation of an electrically insulating contact structure.

In this Thesis I have investigated the use of nanostructured films as sensing and contact layers for field effect gas sensors in order to achieve high sensitivity, selectivity, and long term stability of the devices in corrosive environments at elevated temperatures. Electrochemically synthesized Pd and Au nanoparticles deposited as sensing layers on capacitive field effect devices were found to give a significant response to NOx with small, or no responses to H2, NH3, and C3H6. Pt nanoparticles incorporated in a TiC matrix are catalytically active, but the agglomeration and migration of the Pt particles towards the substrate surface reduces the activity of the sensing layer. Magnetron sputtered epitaxial films from the Ti-Si-C and the Ti-Ge-C systems were grown on 4H-SiC substrates in order to explore their potential as high temperature stable ohmic contact materials to SiC based field effect gas sensors. Ti3SiC2 thin films deposited on 4H-SiC substrates were found to yield ohmic contacts to n-type SiC after a high temperature rapid thermal anneal at 950 ºC. Investigations on the growth mode of Ti3SiC2 thin films with varying Si content on 4H-SiC substrates showed the growth to be lateral step-flow with the propagation of steps with a height as small as half a unit cell. The amount of Si present during deposition leads to differences in surface faceting of the films and Si-supersaturation conditions gives growth of Ti₃SiC₂ films with the presence of TiSi2 crystallites. Current-voltage measurements of the as-deposited Ti₃GeC₂ films indicate that this material is also a promising candidate for achieving long term stable contact layers to 4H-SiC for operation at elevated temperatures in corrosive environments. Further investigations into the Ti-Ge-C system showed that the previously unreported solid solutions of (Ti,V)₂GeC, (Ti,V)₃GeC₂ and (Ti,V)₄GeC₃ can be synthesized, and it was found that the growth of these films is affected by the nature of the substrate.

Epitaxial Ti3SiC2 (0001) thin film contacts were grown on doped 4H-SiC (0001) using magnetron sputtering in an ultra high vacuum system. The specific contact resistance was investigated using linear transmission line measurements. Rapid thermal annealing at 950 degrees C for 1 min of as-deposited films yielded ohmic contacts to n-type SiC with contact resistances in the order of 10(-4) Omega cm(2). Transmission electron microscopy shows that the interface between Ti3SiC2 and n-type SiC is atomically sharp with evidence of interfacial ordering after annealing.

Phase-pure epitaxial thin films of (Ti,V)(2)GeC have been grown onto Al(2)O(3)(0001) substrates via magnetron sputtering. The c lattice parameter is determined to be 12.59 A, corresponding to a 50/50 Ti/V solid solution according to Vegards law, and the overall (Ti,V): Ge: C composition is 2:1:1 as determined by elastic recoil detection analysis. The minimum temperature for the growth of (Ti,V)(2)GeC is 700 degrees C, which is the same as for Ti(2)GeC but higher than that required for V(2)GeC (450 degrees C). Reduced Ge content yields films containing (Ti,V)(3)GeC(2) and (Ti,V)(4)GeC(3). These results show that the previously unknown phases V(3)GeC(2) and V(4)GeC(3) can be stabilized through alloying with Ti. For films grown on 4H-SiC(0001), (Ti,V)(3)GeC(2) was observed as the dominant phase, showing that the nucleation and growth of (Ti,V)(n+1)GeC(n) is affected by the choice of substrate; the proposed underlying physical mechanism is that differences in the local substrate temperature enhance surface diffusion and facilitate the growth of the higher-order phase (Ti,V)(3)GeC(2) compared to (Ti,V)(2)GeC.

Epitaxial Ti3SiC2(0 0 0 1) films were deposited on 4 degrees off-cut 4H-SiC(0 0 0 1) wafers using magnetron sputtering. A lateral step-flow growth mechanism of the Ti3SiC2 was discovered by X-ray diffraction, elastic recoil detection analysis, atomic force microscopy and electron microscopy. Helium ion microscopy revealed contrast variations on the Ti3SiC2 terraces, suggesting a mixed Si and Ti(C) termination. Si-rich growth conditions results in Ti3SiC2 layers with pronounced {1 1 (2) over bar 0) faceting and off-oriented TiSi2 crystallites, while stoichiometric growth yields truncated {1 (1) over bar 0 0) terrace edges.

Thin films in the Ti-Pt-C system were deposited by non-reactive, DC-magnetron sputtering. Samples were characterised using X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy. A previously not reported metastable solid solution carbide, (Ti1-xPtx)C-y with a Pt/Ti ratio of up to 0.43 was observed. This solid solution phase was present both as single phase in polycrystalline samples, and together with amorphous carbon (a-C) in nanocomposite samples. Annealing of nanocomposite samples leads to the decomposition of the solid solution phase and the formation of a nc-TiCx/a-C/nc-Pt nanocomposite. Test sensors for automotive gas exhausts manufactured from such a three-phase material suffer from complete oxidation of the coating at 400 degrees C with no observed sensor activity.

Progresses of synthetic chemistry methodologies have allowed the preparation of a great variety of artificial receptors that are particularly appealing for chemical sensor development. In this paper, we investigate and compare the properties of gas sensors based on two types of devices, quartz microbalances (QMBs) and field effect transistors (FETs), which give the means to exploit the molecular recognition events occurring in non-conductive sensing layers formed by a thiol-modified cobalt tetraphenylporphyrin (CoTPPSH). Since QMB is sensitive to mass and FET is sensitive to electric dipoles, the resulting sensors are expected to exhibit different sensitivities and selectivities, although both based on the same sensing layer. In particular we show that the high sensitivity of CoTPPSH-coated FETs towards CO and NO is a consequence of the significant CoTPPSH electric dipole change after the gas coordination to the metal centre.