Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method combining mechanosynthesis and SPS has been patented in the framework if this study. The controlled etching of 80GeSe₂-20Ga₂Se₃ glass-ceramics in acid solution yields nanoporous materials with enhanced surface area. The porous layer created on the surface of the glass-ceramic is shown to play the role of anti-reflection coating and increase the optical transmission in the infrared range by up to 10%. These materials may have potential for the production of sensors with increased sensitivity in the infrared. The influence of indium and lead addition on the thermal and optical properties of the 80GeSe₂-20Ga₂Se₃ glass has also been assessed. Increased In or Pb contents tend to decrease the Tg of the glasses and shift the optical band gap toward higher wavelengths. A systematic ceramization study emphasizes the difficulty of controlling the crystallization for glasses in the systems GeSe₂-Ga₂Se₃-In₂Se₃ and GeSe₂-Ga₂Se₃-PbSe. No crystallization of the In₂Se₃ and PbSe crystalline phase was obtained. Finally, the possibility of producing rare-earth doped 80GeSe₂-20Ga₂Se₃ glass-ceramics transparent in the infrared region up to 16 μm is demonstrated. Enhanced photoluminescence intensity and reduced radiative lifetimes are observed with increased crystallinity in these materials.

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VO2-based films are thermochromic and exhibit high or low infrared transmittance when the temperature is below or above a critical temperature. The thermochromic switching is passive and reversible, and therefore VO2 based films are promising for energy-efficient window appli­cations. However the practicaluse of VO2 for energy-efficient windows has long been hampered by low luminous transmittance and low solar energy transmittance modulation. The main goal of this dissertation work is to address these issues. The first half of the work proposes the concept of nanothermochromics for simultaneous improvement of luminous transmittance and modulation of solar energy throughput. nanoth­ermochromics considers VO2 nanoparticle composite layers, whose optical properties were modeled by effective medium theories. Calculations on VO2 spheroids have shown that VO2 nanoparticles, especially nanospheres, can offer dramatically improved luminous transmittance and solar transmittance modulation that are not possible for films. Calculations done on coreshell nanoparticles showed comparable improvements and offer an opportunity to reduce the material costs. It was also found that the composite of In2O3:Sn (ITO) and VO2 can yield moderately high luminous transmittance, solar transmittance modulation and low-emittance properties. In the second half of the dissertation work, Mg-doped VO2 films were sputter deposited. Their band gaps and Mg-content were investigated by means of optical absorption measurement and Rutherford backscattering spectrometry, respectively. The band gaps of VO2 were found to increase by ∼3.9±0.5 eV per unit of atom ratio Mg/(Mg+V) for 0<Mg/(Mg+V)<0.21. Computations based on effective medium theory were done to estimate the performance of Mg­-doped VO2 films and nanoparticle composite layers. The results suggest that moderately doped VO2 films with 0<Mg/(Mg+V)<0.06 perform better than un-doped films and that the perfor­mance can be further enhanced with one layer of antireflection coating. The best results were achieved by un-doped VO2 nanospheres, closely followed by the VO2 nanospheres with low Mg-content. Furthermore, the an experimental study on sputter deposited VO2 nanorods has identified the geometry of the oxygen gas inlet, the type of substrate, the substrate temperature and the layer thickness as important factors that influence the growth morphology. Taken as a whole, nanothermochromics offered by VO2 nanoparticles was shown to be the best solution for VO2 based thermochromic energy-efficient window coatings.

The doping concentration and resistivity of tin doped Gallium arsenide nanowires (GaAs NWs) have been investigated using Hall effect-, 4-probe-, transmission line-, and field effect measurements. Single nanowires were contacted using electron beam lithography followed by thermal evaporation of Au/Ti (900/100 Å). The Sn precursor (TESn) molar ratios of the investigated nanowires were 8.5·10-7, 1.7·10-6, 3.4·10-6 and 6.8·10-6 resulting in doping concentrations ranging from 4.64·1013 to 2.11·1017 cm-3 and resistivities from ~0.01 to ~1 Ωcm. The yield of the device fabrication was 2.4-7.1 % and evaluation of additional samples should be done in order to establish the validity of the results. The contact material was proved to work well with the higher doped samples but non-ohmic, highly resistive behavior was seen in the lower doped devices. A resistivity gradient along the length of the nanowires was found to be present, most likely the result of a doping gradient. The sample series with TESn molar ratio 1.7·10-6 showed more tapering than the other series possibly leading to a highly doped shell, which was indicated by 4-probe measurements.

Memoria (licenciado en ciencias jurídicas y sociales)

The key challenge for a nanomaterial based sensor is how to synthesize in bulk quantity and fabricate an actual device with insightful understanding of operational mechanisms during performance. I report here effective, controllable methods that exploit the concepts of the "green approach" to synthesize two different one-dimensional nanostructures, including tin oxide nanowires and carbon nanotubes. The syntheses are followed by product characterization and sensing device fabrications as well as sensor performance understanding at the molecular level. Sensor-analyte response and recovery kinetics are also presented. The first part of the thesis describes bulk-scale synthesis and characterization of tin oxide nanowires by the molten salt synthetic method and the nanowire doping with antimony (n-types) and lithium. The work builds on the success of using n-doped SnO2 nanoparticles to selectively detect chlorine gas at room temperature. Replacing n-doped nanoparticles with n-doped nanowires reduces the number of inter-particle electron hops between sensing electrodes. The nanowire based sensors show unprecedented 5 ppb detectability of corrosive Cl2 gas concentration in air. At the higher range, 10 ppm of Cl2 gas leads to a 250 fold increase in the device resistance. During sensor recovery, FT-IR studies show that dichlorine monoxide (Cl2O) and chlorine dioxide (ClO2) are the desorbing species. Long term stability of devices is affected by lattice oxygen vacancies replaced by chlorine atoms. Bulk-scale synthesis of multiwall carbon nanotube (MWCNTs) was achieved by a novel inexpensive synthetic method. The green chemistry method uses the non-toxic and easy to handle solid carbon source naphthalene. The synthesis is carried out by simply heating naphthalene and organometallic precursors as catalysts in a sealed glass tube. Synthesis at 610º C leads to MWCNTs of 50 nm diameter and lengths exceeding well over microns. MWCNT doping is attempted with nitrogen (n-type) and boron (p-type) precursors. Palladium nanoparticles decorated on as-synthesized MWCNTs are employed for specific detection of explosive hydrogen gas with concentrations far below the explosive concentration limits. During performance, the sensor exhibits abnormal response behaviors at hydrogen gas concentrations higher than 1%. A model of charge carrier inversion, brought about by reduction of MWCNT by hydrogen molecules dissociated by Pd nanoparticles is proposed.