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Rare-earth activated upconversion material is receiving renewed attention for their potential applications in bioimaging and solar energy conversion. Plasmon resonance can enhance the upconversion efficiency but the enhancement mechanism remained unclear due to the inherent complexity of upconversion process.
In this study, we synthesized NaYF4:Yb3+,Er3+ upconversion nanoparticles (UCNPs) and modified the surface with an amphiphilic polymer, (poly(maleic anhydride-alt-octadecene) (PMAO), which makes UCNPs water-soluble and negatively charged. This in turn enables electrostatic self-assembly of UCNPs. We fabricated silver nanograting using laser-interference lithography and deposited 3 monolayers of UNCPs by polyelectrolyte-mediated layer-by-layer self-assembly process. It is noted that all the fabrication processes are scalable.
We then conducted a comprehensive photoluminescence (PL) and transient PL spectroscopy. We observed up to 39x enhancement in PL intensity. A combination of numerical simulations, rate equation analysis and transient PL spectroscopy revealed that the total enhancement is made of 3.1x absorption enhancement and 2.7x energy transfer rate enhancement. The absorption enhancement makes the most contribution because the upconverted PL intensity varies quadratically with the absorption. This study represents the first experimental observation of plasmon enhanced energy transfer rate in UCNPs. It contributes to the long debate on the plasmon enhancement of Förster energy transfer process.
Finally, we developed a new numerical modeling tool that can faithfully simulate the highly non-uniform light absorption and carrier generation in the plasmon enhanced photovoltaic devices. We used the tool to precisely predict the performance of photovoltaic devices incorporating plasmon enhanced upconversion and offer guidelines for upconversion photovoltaic devices.
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