Concentrating and Recycling Energy in Lanthanide Codopants for Efficient and Spectrally Pure Emission: The Case of NaYF₄:Er3+/Tm3+ Upconverting Nanocrystals

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Abstract

In lanthanide-doped materials, energy transfer (ET) between codopant ions can populate or depopulate excited states, giving rise to spectrally pure luminescence that is valuable for the multicolor imaging and simultaneous tracking of multiple biological species. Here, we use the case study of NaYF(4) nanocrystals codoped with Er(3+) and Tm(3+) to theoretically investigate the ET mechanisms that selectively enhance and suppress visible upconversion luminescence under near-infrared excitation. Using an experimentally validated population balance model and using a path-tracing algorithm to objectively identify transitions with the most significant contributions, we isolated a network of six pathways that combine to divert energy away from the green-emitting manifolds and concentrate it in the Tm(3+):(3)F(4) manifold, which then participates in energy transfer upconversion (ETU) to populate the red-emitting Er(3+):(4)F(9/2) manifold. We conclude that the strength of this ETU process is a function of the strong coupling of the Tm(3+):(3)F(4) manifold and its ground state, the near-optimum band alignment of Er(3+) and Tm(3+) manifolds, and the concentration of population in Tm(3+):(3)F(4). These factors, along with the ability to recycle energy not utilized for red emission, also contribute to the enhanced quantum yield of NaYF(4):Er(3+)/Tm(3+). We generalize a scheme for applying these energy concentration and recycling pathways to other combinations of lanthanide dopants. Ultimately, these ET pathways and others elucidated by our theoretical modeling will enable the programming of physical properties in lanthanide-doped materials for a variety of applications that demand strong and precisely defined optical transitions.

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