New Polymer and Composite Structures for Photonic Applications

The focus of this thesis is the development of materials and architectures for all-polymer functional structures for photonic applications. The first part concerns the improvement and optimization of colorimetric and fluorescent sensing structures for the detection of various analytes in the vapor phase. Optical-readout sensors are portable and can provide an easy interpretation that needs no specialized training and can be visible to the naked eye. This makes them promising for applications in environmental control, health monitoring and food safety. The objective of the work was to investigate analyte diffusion processes into multilayered structures of polymer submicrometric films, and then optimizing the structure design and expanding the materials used in the field. First, sensors based on vapor diffusion in multilayered polymer dielectric mirrors with structural coloring were developed. Given their clear color change, this typology of sensors has been shown to be promising in the literature. However, as their response is limited by the diffusion speed of molecular species, they can suffer from slow detection of vapor-phase analytes. Next, I examine the use of fluorescent polymer films sensitive to microviscosity changes caused by exposure to volatile organic compounds and observing the changes in fluorescence during said exposure. The effect on the overall diffusion of capping layers deposited on top of the fluorescent polymer was investigated to quantify the effect of the barrier polymer on the selectivity of the sensor. Finally, I employed the solution processing protocols developed for novel low refractive index polymer suspensions that were initially utilized for the sensors to engineer structures for fluorescence control. When two highly reflecting structures encapsulate a luminescent material in a submicrometric space, this changes the photoluminescence properties in structures called optical microcavities. While the highly reflecting structures can be metallic mirrors, these have limited reflectance intensity, high absorbance losses, as well as a lack of tunability. Instead, the use of dielectric mirrors enables very high reflectance at desired wavelengths. In addition, the use of compliant polymer materials allows the future use of these structures to construct more efficient flexible devices. I was able to develop highly reflecting microcavities for emitters in the visible range as well as in the near infrared. Besides achieving high amplification of fluorescence intensity, I was also able to report for the first time a change in the radiative rate of the fluorescence for polymer structures. As these effects were so far only observed in planar structures of inorganic nature or more complex polymer three-dimensional systems, this presents a breakthrough in the field. In this introduction I will give a wide but deep overview of the optics of multilayered polymer films, their diffusion peculiarities, and use for sensing. Furthermore, I will address the topic of solid-state organic fluorophores and controlling their photoluminescence through engineering the dielectric environment. This will be followed by a chapter-by-chapter exploration of the results obtained during the doctoral training as adapted from already published or drafted work. Finally, the outlook and possible future implications and developments of this research will be examined.