Biluminescence of purely organic materials: fundamentals and applications in optical sensing

Manifestación

Autores
Identificador
1162874
Fecha de publicación
2017; 2014; 2015; 2020; 2021; 2009
Forma obra
Tesis
Lugar de producción
2017; 2014; 2015; 2020; 2021; 2009
Nota de edición
Digitalización realizada por la Biblioteca Virtual del Banco de la República (Colombia)
Materias
  • Ciencias naturales y matemáticas; Ciencias naturales y matemáticas / Física
  • Organic; Semiconductor; Optical sensor; Biluminescence; BILUM; Simultaneous dual-state emitter; Singlet-triplet annihilation; Triplet-triplet annihilation; STA; TTA; Room temperature; Phosphorescence; RTP; Semiconductor physics
Notas
  • Colombia
  • Colfuturo
  • © Derechos reservados del autor
  • Abstract: The property of an organic molecule able to emit light efficiently from both their singlet and triplet excited states is called biluminescence. This dual state emission, particularly at room temperature, is difficult to achieve by purely organic molecules. It is possible only if the competitive thermal decay is suppressed effectively, enhancing the yield from the triplet state (i.e. phosphorescence) in addition to the conventional fluorescence. Biluminescence was identified in a simple host:guest system in which the biluminophore (i.e. an organic molecule showing biluminescence) NPB [N,N’-di(naphtha-1-yl)-N,N’- diphenyl-benzidine] is embedded in a rigid matrix, for example, the polymer PMMA [poly(methyl methacrylate)]. This system is unique not only due to the dual state emission, having fluorescence and phosphorescence emissions at 425nm and 530nm, respectively, but also because the large range of exciton lifetimes is extended up to nine orders of magnitude between nanosecond fluorescence and second phosphorescence. Up to date, efforts have been placed exclusively in the research of room temperature phosphorescence (RTP), although fluorescence can be observed from these systems as well. Therefore, the aim of this thesis was the investigation of the fundamental photophysical processes and characteristics of biluminescent organic molecules, in addition to their usage in promising applications as it will be described next. For instance, the most used approach for oxygen sensing is based on quenching of luminescent excited states, following a scheme of optical monitoring, i.e. correlating luminescence over-time data with oxygen concentrations. However, regardless whether one pursues fluorescence or phosphorescence quenching, they share a common drawback: They cannot monitor the effect of sample degradation due to extensive light exposure. In fact, one cannot distinguish between oxygen having penetrated the film and quenched the luminescence, or the sample being degraded over time due to e.g. photobleaching of the emitting molecules. The former represents an issue, especially for build-in applications. Now herein, it was proposed to use biluminescence to exclude degradation processes from oxygen sensing data evaluation, through a simple fluorescence-to-phosphorescence intensity ratio. This can be achieved, because it was proven here that the fluorescence is not directly quenched by oxygen, whereas the long-lived RTP is sensitive to it. Therefore, the fluorescence acts as self-referencing in a biluminescent sensor, which serves as an alternative solution to monitor oxygen concentrations. Additionally, the integration of the sensor into optoelectronic devices is considered as a potential future direction. Furthermore, it was revealed in this thesis that the difference in exciton lifetime yields to a significant limitation of luminescence efficiency, because of exciton accumulation under continuous illumination, causing bimolecular processes like singlet-triplet and triplet-triplet annihilation (STA and TTA, respectively), as well as optical saturation. All those processes occur already at moderate excitation intensities. It was demonstrated through sample engineering and oxygen quenching experiments, that the triplet exciton density can be controlled over several orders of magnitude, allowing to study exciton interactions between singlet and triplet manifolds. Consequently, the presented biluminescent system represents an illustrative role model to study excitonic effects in organic molecules. For example, in organic light-emitting diode materials, where the aforementioned effects i.e. STA, TTA and saturation, are application relevant but much more difficult to investigate. Mainly because light emission can be observed only from one state, instead of both states like in biluminescence.
Enlace permanente
https://www.cervantesvirtual.com/obra/biluminescence-of-purely-organic-materials-fundamentals-and-applications-in-optical-sensing-1162874
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