Improper Background Treatment Underestimates Thermometric Performance of Rare Earth Vanadate and Phosphovanadate Nanocrystals.

Abstract

Luminescence thermometry is the state-of-the-art technique for remote nanoscale temperature sensing, offering numerous promising cutting-edge applications. Advancing nanothermometry further requires rational design of phosphors and well-defined, comprehensive mathematical treatment of spectral information. However, important questions regarding improper signal processing in ratiometric luminescence thermometry are continuously overlooked in the literature. Here, we demonstrate that systematic errors arising from background/signal superposition impact the calculated thermometric quality parameters of ratiometric thermometers. We designed ultraviolet-excitable (Y,Eu)VO4 and (Y,Eu)(P,V)O4 nanocrystals showing overlapped VO4 3- and Eu3+ emissions to discuss systematically how uncorrected background emissions cause magnified (∼10×) temperature uncertainties and undervalued (∼60%) relative thermal sensitivities. Adequate separation of spectral contributions from the VO4 3- background and the Eu3+ signals via baseline correction is necessary to prevent underestimation of the thermometric performances. The described approach can be potentially extended to other luminescent thermometers to account for signal superposition, thus enabling to circumvent computation of apparent, miscalculated thermometric parameters.