Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.

Novel smart modules for imaging, communications, and displays

This dissertation proposes and demonstrates novel smart modules to solve challenging problems in the areas of imaging, communications, and displays. The smartness of the modules is due to their ability to be able to adapt to changes in operating environment and application using programmable devices, specifically, electronically variable focus lenses (ECVFLs) and digital micromirror devices (DMD). The proposed modules include imagers for laser characterization and general purpose imaging which smartly adapt to changes in irradiance, optical wireless communication systems which can adapt to the number of users and to changes in link length, and a smart laser projection display that smartly adjust the pixel size to achieve a high resolution projected image at each screen distance. The first part of the dissertation starts with the proposal of using an ECVFL to create a novel multimode laser beam characterizer for coherent light. This laser beam characterizer uses the ECVFL and a DMD so that no mechanical motion of optical components along the optical axis is required. This reduces the mechanical motion overhead that traditional laser beam characterizers have, making this laser beam characterizer more accurate and reliable. The smart laser beam characterizer is able to account for irradiance fluctuations in the source. Using image processing, the important parameters that describe multimode laser beam propagation have been successfully extracted for a multi-mode laser test source. Specifically, the laser beam analysis parameters measured are the M2 parameter, w0 the minimum beam waist, and zR the Rayleigh range. Next a general purpose incoherent light imager that has a high dynamic range (>100 dB) and automatically adjusts for variations in irradiance in the scene is proposed. Then a data efficient image sensor is demonstrated. The idea of this smart image sensor is to reduce the bandwidth needed for transmitting data from the sensor by only sending the information which is required for the specific application while discarding the unnecessary data. In this case, the imager demonstrated sends only information regarding the boundaries of objects in the image so that after transmission to a remote image viewing location, these boundaries can be used to map out objects in the original image. The second part of the dissertation proposes and demonstrates smart optical communications systems using ECVFLs. This starts with the proposal and demonstration of a zero propagation loss optical wireless link using visible light with experiments covering a 1 to 4 m range. By adjusting the focal length of the ECVFLs for this directed line-of-sight link (LOS) the laser beam propagation parameters are adjusted such that the maximum amount of transmitted optical power is captured by the receiver for each link length. This power budget saving enables a longer achievable link range, a better SNR/BER, or higher power efficiency since more received power means the transmitted power can be reduced. Afterwards, a smart dual mode optical wireless link is proposed and demonstrated using a laser and LED coupled to the ECVFL to provide for the first time features of high bandwidths and wide beam coverage. This optical wireless link combines the capabilities of smart directed LOS link from the previous section with a diffuse optical wireless link, thus achieving high data rates and robustness to blocking. The proposed smart system can switch from LOS mode to Diffuse mode when blocking occurs or operate in both modes simultaneously to accommodate multiple users and operate a high speed link if one of the users requires extra bandwidth. The last part of this section presents the design of fibre optic and free-space optical switches which use ECVFLs to deflect the beams to achieve switching operation. These switching modules can be used in the proposed optical wireless indoor network. The final section of the thesis presents a novel smart laser scanning display. The ECVFL is used to create the smallest beam spot size possible for the system designed at the distance of the screen. The smart laser scanning display increases the spatial resoluti on of the display for any given distance. A basic smart display operation has been tested for red light and a 4X improvement in pixel resolution for the image has been demonstrated.

Characterisation and spectroscopy of laser-cooled atoms with an optical nanofibre

In this thesis, a magneto-optical trap setup is used to laser cool and confine a cloud of 85Rb. The cloud typically contains 108 atoms in a 1 mm3 volume at a temperature in the region of the Doppler Limit (146 _K for 85Rb). To study the cold cloud, a subwavelength optical fibre - a nanofibre, or ONF - is positioned inside the cloud. The ONF can be used in two ways. Firstly, it is an efficient fluorescence collection tool for the cold atoms. Loading times, lifetimes and temperatures can be measured by coupling the atomic fluorescence to the evanescent region of the ONF. Secondly, the ONF is used as a probe beam delivery tool using the evanescent field properties of the device, allowing one to perform spectroscopy on few numbers of near-surface atoms. With improvements in optical density of the cloud, this system is an ideal candidate in which to generate electromagnetically induced transparency and slow light. A theoretical study of the van der Waals and Casimir-Polder interactions between an atom and a dielectric surface is also presented in this work in order to understand their effects in the spectroscopy of near-surface atoms.