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      Photophysical Studies of Photon Upconversion via Triplet-Triplet Annihilation in Polymer Systems with Potential Photovoltaic Applications

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      BOUTIN-THESIS.pdf (2.642Mb)
      Date
      2014-06-11
      Author
      Boutin, Philip C.
      Type
      Thesis
      Degree Level
      Masters
      Metadata
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      Abstract
      The present work reports the study of noncoherent photon upconversion (NCPU) via triplet-triplet annihilation (TTA) in polymer systems. This upconversion mechanism has application in photovoltaic devices through the utilization of sub-band gap photons for potentially enhanced power conversion efficiencies. First, homomolecular TTA was studied in zinc tetraphenylporphyrin (ZnTPP) in polymer matrices. Here, ZnTPP acts as both the sensitizer and upconverting emitter as TTA yields an S2 excited porphyrin. Use of poly(methyl methacrylate) (PMMA) as the host polymer demonstrates aggregation-driven upconverted fluorescence (UC) by TTA (TTA-UC). The dye-loading ratio of the precursor solution was varied, controlling the degree of pre-aggregation. Power-dependence studies of the champion film demonstrated that TTA-UC is occurring toward the strong annihilation kinetic limit. A sub-linear dependence of upconverted fluorescence on film thickness was observed in this system. The ZnTPP study was extended to polymers possessing low glass transition temperatures, representing molecular diffusion-driven TTA-UC. Upconverted fluorescence was not observed in ZnTPP in a polyurethane (PU) matrix, likely due to coordination of the PU to the axial position of the Zn2+ ion. Low intensity NCPU via homomolecular TTA was observed in ZnTPP in a poly(ethylene glycol) (PEG) matrix, but the kinetic limit was not determined due to film photodegradation. Dye-loading studies revealed that porphyrin self-quenching was evident at low dye concentrations. Likely reasons for the low upconverted fluorescence intensities realized are this self-quenching and the possibility of PEG coordination to the Zn2+ ion, though it is believed self-quenching is the dominant parasitic effect. Strategies to determine the effect and extent of polymer coordination to the Zn2+ ion are discussed. The study of polymer-based NCPU is extended to a pair of macromolecules, each containing a single ruthenium tris(bipyridine) (Ru(bpy)3) core and multiple pendant arms, which in turn, each contain eight 9,10-diphenylanthracene (DPA) moieties. A power-dependence study of NCPU in this system is reported, and TTA-UC in the weak annihilation kinetic limit was observed. Upconverted fluorescence quantum yields vary linearly with excitation power in both polymers, consistent with the observed kinetic limit. Stern-Volmer experiments have compared the quenching of Ru(bpy)3 phosphorescence (Ph) by monomeric and polymeric DPA. These data show an enhancement in quenching rate constant for the DPA polymer (pDPA). Kinetic analysis of the Ru-DPA polymers has revealed that the energy scheme realized in this system is intrachain TTET from Ru(bpy)3 core to DPA emitter followed by interchain TTA between excited DPA moieties. Low intensity upconverted fluorescence is observed in Ru-DPA containing thin films. Based on the results presented, the requirements of future photophysically-active polymers are discussed with regards to meaningful application in photovoltaics.
      Degree
      Master of Science (M.Sc.)
      Department
      Chemistry
      Program
      Chemistry
      Supervisor
      Steer, Ronald P.; Kelly, Timothy L.
      Committee
      Paige, Matthew F.; Yao, Yansun
      Copyright Date
      April 2014
      URI
      http://hdl.handle.net/10388/ETD-2014-04-1509
      Subject
      Keyword 1
      Photon Upconversion
      Keyword 2
      Triplet-Triplet Annihilation
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