Quantitative Photothermal Heating and Cooling Measurements of Engineered Nanoparticles in an Optical Trap

Abstract

Laser tweezers and optical trapping has provided scientists and engineers a unique way to study the wealth of phenomena that materials exhibit at the micro- and nanoscale, much of which remains mysterious. Of particular interest is the interplay between light absorption and subsequent heat generation of laser-irradiated materials, especially due to recent interest in developing nanoscale materials for use as agents for photothermal cancer treatments. An introduction to optical trapping physics and laser tweezers are given in Chapter 1 and 2 of this thesis, respectively. The remaining chapters, summarized below, describe the theoretical basis of laser heating of one-dimensional nanostructures and experiments in which optically-trapped nanostructures are studied using techniques developed for a laser tweezer. In Chapter 3, we delve into the fundamentals of laser heating of one-dimensional materials by developing an analytical model of pulsed laser heating of uniform and tapered supported nanowires and compare calculations with experimental data to comment on the effects that the material's physical, optical, and thermal parameters have on its heating and cooling rates. We then consider closed-form analytical solutions for the temperature rise within infinite circular cylinders with nanometer-scale diameters irradiated at right angles by TM-polarized continuous-wave laser sources, which allows for analysis of laser-heated nanowires in a solvated environment. The infinite nanowire analysis will then be extended to the optical heating of laser-irradiated finite nanowires in the framework of a laser tweezer, which enables predictive capabilities and direct comparison with laser trapping experiments. An effective method for determining optically-trapped particle temperatures as well as the temperature gradient in the surrounding medium will be discussed in Chapter 4. By combining laser tweezer calibration techniques, forward-scattered light power spectrum analysis, and hot Brownian motion theory, we attempt to measure realistic temperatures at the surface of an optically-trapped particle while properly accounting for inhomogeneous temperature fields generated by the optical trap. In Chapter 5, this technique is then applied to measure the temperature of engineered gold- and silicon-implanted silicon nanowires to rigorously study the effect ion implantation has on silicon nanowire photothermal efficiencies. Silicon nanowire photothermal efficiencies are shown to drastically increase by implanting with gold ions and cause superheating of water of over 200 C at the trap site, suggesting potential application as agents for photothermal cancer therapies. Chapter 6 describes the hydrothermal synthesis and optical trapping of engineered YLF nanoparticles doped with Yb(III) ions. Laser tweezer experiments using the developed temperature extraction techniques and hot Brownian motion analysis show the first observation of particles undergoing recently hypothesized cold Brownian motion and local laser refrigeration in a condensed phase via anti-Stokes photoluminescence. Furthermore, YLF nanoparticles codoped with Er(III) and Yb(III) ions are also developed and their intense visible upconversion of the NIR trapping laser is used to monitor its internal lattice temperature using ratiometric thermography. The results suggest the potential of these materials to investigate kinetics and temperature sensitivity of basic cellular processes, or to act as simultaneous theranostic-hypothermia agents to identify and treat cancerous tissues. Finally, Chapter 7 presents a summary of the salient conclusions of the reported studies. The chapter concludes with a short discussion of my personal experience with being a member of a new research group and setting up the Pauzauskie laboratory.