Energy pooling upconversion in free space and optical cavities

Abstract

The ability to efficiently convert the wavelength of light has value in a wide range of disciplines that include the fields of photovoltaics, plant growth, optics and medicine. The processes by which such transformations are carried out are known as upconversions and downconversions. There are several ways to up/down convert light, each with its own attributes, issues, and competing mechanisms. Most are associated with one-body or two-body processes. Three-body dynamics are also possible though, going by the names of quantum cutting (downconversion) and energy pooling (upconversion). These use virtual excited electronic states to mediate conversions as has been experimentally realized using lanthanide ions embedded in wide bandgap materials. The use of lanthanides to convert light is not ideal due to their relative scarcity, toxicity, and the limited range of light frequencies that can be absorbed and emitted. Organic molecules, on the other hand, are typically non-toxic, are made up of abundant elements, and can be designed with tailored spectral properties. At issue is whether or not they can be used to carry out efficient energy pooling, the central question to be answered in this thesis. The research presented here draws on a perturbative quantum electrodynamics framework previously established for generic energy pooling. It was used to develop a computational methodology for determining the rate of energy pooling and its competing processes. This, in turn, draws on a combination of time-dependent density functional theory, quantum electrodynamics, and perturbation theory to generate the requisite material property data. This computational model was applied to two test systems consisting of stilbene-fluorescein and hexabenzocoronene-oligothiophene. The stilbene-fluorescein system was found to have a maximum energy pooling rate efficiency (as compared to competing processes) of 17% and the hexabenzocoronene-oligothiophene system was found to have a maximum energy pooling rate efficiency of 99%. This demonstrates that the energy pooling rate can be made faster than its competing processes. Based on the results of this study, a set of design rules was developed to optimize the rate efficiency of energy pooling. Prior to this research, no attempt had been made to determine if energy pooling could be made to out-pace competing processes---i.e. whether or not a molecular system could be designed to utilize energy pooling as an efficient means of upconversion. This initial investigation was part of a larger effort involving a team of researchers at the University of Colorado, Boulder and at the National Renewable Energy Laboratory. After establishing our computational proof-of-concept, we collectively used the new design rules to select an improved system for energy pooling. This consisted of rhodamine 6G and stilbene-420. These molecules were fabricated into a thin film, and the maximum internal quantum yield was measured to be 36% under sufficiently high intensity light. To further increase the efficiency of energy pooling, encapsulation within optical cavities was considered as a way of changing the rate of processes characterized by electric dipole-dipole coupling. This was carried out using a combination of classical electromagnetism, quantum electrodynamics, and perturbation theory. It was found that, in the near field, if the distance of the energy transfer is smaller than the distance from the energy transfer site and the cavity wall, then the electric dipole-dipole coupling tensor is not influenced by the cavity environment and the rates of energy transfer processes are the same as those in free space. Any increase in energy transfer efficiencies that are experimentally measured must therefore be caused by changing the rate of light absorption and emission. This is an important finding because earlier, less rigorous studies had concluded otherwise. It has been previously demonstrated that an optical cavity can be used to inhibit the spontaneous emission of atoms or molecules placed within it. This too was examined as a possible means of increasing energy pooling efficiency. Using first-principles methods, quantum electrodynamics, perturbation theory, and a kinetic model, the efficiency of energy pooling upconversion within a tuned rectangular cavity was found to be significantly larger than in free space. A model system with a free-space energy pooling upconversion efficiency of 23% was found to increase to 47% when placed in a tuned rectangular cavity.