Title: Photon avalanching in Tm³⁺
Description: Photon avalanching (PA), one of the more unique nonlinear optical processes due to its combination of efficiency and extreme response, first attracted attention from the optics community more than four decades ago. But interest waned as researchers found that it did not provide immediately useful features observed in other nonlinear optical systems, such as amplified coherent light generation from lasing or optoelectronic amplification and transduction afforded by light-stimulated electron avalanching. The material systems supporting PA were also found to be rather limited, with reports concentrating on fragile, bulk lanthanide-doped crystals. However, the inter-ionic energy transfer mechanisms responsible for PA and its extreme nonlinearity are, in principle, realizable in objects with dimensions at the nanoscale. Further, new applications for PA in nanomaterials including simple super-resolution microscopy have recently been proposed. These factors motivated my research on the development of the first-ever lanthanide-doped nanoparticles capable of supporting PA behavior.

In this thesis, the optical properties of Tm³⁺-doped NaYF₄ nanocrystals are investigated with photoluminescence microscopy, spectroscopy and differential rate equation model simulations. First, the photon avalanching behavior of Tm³⁺-doped NaYF₄ nanocrystals is studied. Specifically, the excitation-power-dependent luminescence of 1%, 4%, 8%, 20%, and 100% Tm³⁺-doped NaYF₄ is measured. The slopes of log-log excitation intensity versus emission intensity plots show that photon avalanche is realized in the nanocrystals when Tm³⁺ content is 8% and above. Time-resolved luminescence and rate equation model fitting to the experimental data validate the existence of photon avalanche, showing luminescence rise times > 600 ms, and the ratio of the ³F₄-to-³F₃ excited state absorption to the ³H₆-to-³F₄ ground state absorption is > 10⁴, which are signatures of photon avalanche. The design-dependent shift of the photon avalanching threshold also shows that photon avalanche is the main excitation scheme for the nanocrystals and implies potential applications for ultra-sensitive nano-sensing with the help of extreme nonlinearity.

Additionally, the steep nonlinearity leads to super-resolution microscopy of single 8% Tm³⁺-doped nanocrystals with resolution down to <70 nm using conventional confocal microscopy without sophisticated techniques. In the second part of the thesis, the photodarkening effect of Tm³⁺-doped NaYF₄ nanocrystals is studied. We have found that photodarkening behavior is observed in Tm³⁺-doped nanocrystals that exhibit the photon avalanche effect. Power-dependent luminescence of a single 8% Tm3+-doped nanocrystal reveals that photodarkened nanocrystals still support photon avalanche behavior, but the avalanching threshold is shifted to a higher value. A photodarkening mechanism is proposed based on the concentration-dependent and power-dependent luminescence properties, and optical spectroscopic data. Notably, photodarkened nanocrystals are found to recover their original brightness and behavior under Vis-NIR optical illumination. This so-called “photobrightening” allows novel photoswitching of the inorganic nanocrystals, which has never before been achieved.

We observe robust single nanocrystal photoswitching over 1000 cycles without permanent photodegradation. In addition, rewritable photolithography of multiple patterns using NIR lasers at 700 nm and 1064 nm is demonstrated.