Controlling the Thermal Switching in Upconverting Nanoparticles Through Surface Chemistry

Photon upconversion taking place in small rare-earth-doped nanoparticles has been recently observed to be thermally modulated in an anomalous manner, showing thermal enhancement of the emission intensity. This effect was proved to be linked to the role of adsorbed water molecules as surface quenchers. Therefore, the surface capping of the particles has a direct influence on the thermal dynamics of water adsorption and desorption. Here, we show that the upconversion intensity of small-size (<25 nm) nanoparticles co-doped with Yb³⁺ and Er³⁺ ions, and functionalized with different capping molecules, present clear irreversibility patterns upon thermal cycling that strongly depend on the chemical nature of the nanoparticle surface. By performing temperature-controlled luminescence measurements we observed the formation of a thermal hysteresis loop, resembling an optical switching phenomenon, whose shape and trajectory depend on the hydrophilicity of the surface chemistry.  Additionally, the formation of an intensity overshoot takes place immediately after turning off the heating source, affecting each radiative transition differently. We performed numerical modelling to understand this effect considering non-radiative energy transfer from surface defect states to the Er³⁺ ions. These findings are relevant for the comprehension of nanoparticle-based luminescence and the interplay between surface and volume effects, and more generally, for applications involving UCNPs such as nanothermometry, bioimaging, and the development of optical encoding systems.