Influence of the surrounding medium on the luminescence-based thermometric properties of single Yb3+/Er3+ codoped yttria nanocrystals

Abstract

While temperature measurements with nanometric spatial resolution can provide valuable information in several fields, most of the current literature using rare-earth based nanothermometers report ensemble-averaged data. Neglecting individual characteristics of each nanocrystal (NC) may lead to important inaccuracies in the temperature measurements. In this work, individual Yb³⁺/Er³⁺ codoped yttria NCs are characterized as nanothermometers when embedded in different environments (air, water and ethylene glycol) using the same 5 NCs in all measurements, applying the luminescence intensity ratio technique. The obtained results show that the nanothermometric behavior of each NC in water is equivalent to that in air, up to an overall brightness reduction related to a decrease in collected light. Also, it was observed that the thermometric parameters from each NC can be much more precisely determined than those from the “ensemble” equivalent to the set of 5 single NCs. The “ensemble” parameters have increased uncertainties mainly due to NC size-related variations, which we associate to differences in the surface/volume ratio. Besides the reduced parameter uncertainty, it was also noticed that the single-NC thermometric parameters are directly correlated to the NC brightness, with a dependence that is consistent with the expected variation in the surface/volume ratio. The relevance of surface effects also became evident when the NCs were embedded in ethylene glycol, for which a molecular vibrational mode can resonantly interact with the Er³⁺ ions electronic excited states used in the present experiments. The methods discussed herein are suitable for contactless on-site calibration of the NCs thermometric response. Therefore, this work can also be useful in the development of measurement and calibration protocols for several lanthanide-based nanothermometric systems.