Luminescent instabilities and nonradiative processes in rare earth systems

This research is an outgrowth of earlier experiments that demonstrated bistable luminescence in heavy metal halide crystals doped with trivalent ytterbium ions. This type of instability has importance as a fundamentally new physical phenomenon with a potential application for fast all-optical switching as well as a limitation on compact solid state laser performance. In this thesis, the investigation of luminescent instabilities is extended to bistable energy transfer processes in crystals and to the observation of “bistable” blackbody emission in rare earth nanopowders.; High resolution laser spectroscopy was used to study bistable luminescence and energy transfer in Yb,Er:CsCdBr₃ crystals at cryogenic temperatures. For the first time, it was found that bistable behavior associated with Yb 3+ ions was transferred to Er3+ through resonant energy transfer. Bistability of the resulting sensitized luminescence caused sufficiently dramatic changes in the crystal dynamics so as to change the color of emission from yellow to green. This color changing phenomenon is fully explained in the present work and is referred to as “chromatic switching.”; Temperature is a critical variable that is known to govern luminescent instabilities in all current theories. Therefore, in a search for new systems with luminescent instabilities at high temperatures, materials with extreme thermal properties were investigated as part of this research. Yb,Er:Y ₂O₃ nanopowders were selected for this purpose. Nanopowders exhibit greatly reduced thermal conductivity and were verified during the course of this work to cause enhanced absorption as the result of multiple scattering. Significant spectral differences between Yb,Er:Y₂O ₃ nanopowders and single crystals also emerged. Measurements of erbium upconversion luminescence versus pump intensity in resonance with the ytterbium absorption transition revealed striking new optical phenomena: strong luminescent quenching, intense “bistable” blackbody emission, and the formation of single crystal micro-tubes directly from powder samples. A simple theoretical model was successfully developed to explain all these optical effects by a detailed balance approach to thermal transport that explicitly included erbium and ytterbium atomic level occupation probabilities, blackbody radiation and radiation trapping. Calculations of nanopowder sample luminescence accurately reproduced experimentally observed quenching, the onset of blackbody emission, “bistability” and details of hysteresis loops. The model also predicted that absorbed powers of less than 15 mW could melt yttria nanopowders (melting point = 2410°C), again in agreement with experiments.; This work is expected to enable new approaches to laser processing of ceramics and laser machining of reflective metals, notably aluminum, using low power lasers.