Time-resolved universal temperature measurements using NaYF₄:Er³⁺,Yb³⁺ upconverting nanoparticles in an electrospray...

Hexagonal upconverting nanoparticles (UCNPs) of NaYF₄:Er³⁺,Yb³⁺ (ca. 300 nm) have been widely used to measure the temperature at the nanoscale using luminescence ratio thermometry. However, several factors limit their applications. For example, changes in the peak shape, mainly is the S-band emission, hinders their ability to be used as a universal temperature sensor. Herein, we introduce a universal calibration protocol for NaYF₄:Er³⁺,Yb³⁺ upconverting nanoparticles that is robust to environmental changes and gives a precise temperature measurement. We used this new procedure to calculate the temperature profile inside a Taylor cone generated with an electrospray jet. Inside the Taylor cone the fluid velocity increases toward the tip of the cone. A constant acquisition length leads to a decrease in excitation and acquisition time. This decrease in excitation time causes a peak shape change that corrupts the temperature measurement if the entire peak shape is integrated in the calibration. Our universal calibration circumvents this problem and can be used for time-resolved applications. The temperature at the end of the Taylor cone increases due to the creation of a whispering gallery mode cavity with 980 nm excitation. We use time-resolved energy balance equations to support our optical temperature measurements inside the Taylor cone. We believe that the findings of this paper provide a foundation for time-resolved temperature measurements using NaYF₄:Er³⁺,Yb³⁺ upconverting nanoparticles and can be used to understand temperature-dependent reactions such as protein unfolding inside microjet/microdroplets and microfluidic systems.