Upconverting Core-Shell Nanocrystals with High Quantum Yield under Low Irradiance: On the Role of Isotropic and Thick Shells

Abstract: Colloidal upconverter nanocrystals (UCNCs) that convert near-infrared photons to higher energies are promising for applications ranging from life sciences to solar energy harvesting. However, practical applications of UCNCs are hindered by their low upconversion quantum yield (UCQY) and the high irradiances necessary to produce relevant upconversion luminescence. Achieving high UCQY under practically relevant irradiance remains a major challenge. The UCQY is severely limited due to non-radiative surface quenching processes. We present a rate equation model for migration of the excitation energy to show that surface quenching does not only affect the lanthanide ions directly at the surface but also many other lanthanide ions quite far away from the surface. The average migration path length is in the order of several nanometers and depends on the doping as well as the irradiance of the excitation. Using Er3+-doped beta-NaYF4 UCNCs, we show that very isotropic and thick (~10 nm) beta-NaLuF4 inert shells dramatically reduce the surface-related quenching processes, resulting in much brighter upconversion luminescence at simultaneously considerably lower irradiances. For these UCNCs embedded in PMMA, we determined an internal UCQY of 2.0+-0.2 % using an irradiance of only 0.43+-0.03 W/cm2 at 1523 nm. Normalized to the irradiance, this UCQY is 120x higher than the highest values of comparable nanomaterials in the literature. Our findings demonstrate the important role of isotropic and thick shells in achieving high UCQY at low irradiances from UCNCs. Additionally, we measured the additional short-circuit current due to upconversion in silicon solar cell devices as a proof concept and to support our findings determined using optical measurements.