ConspectusThe growing demand for nanoscale temperature measurement capabilities is motivated by diverse applications such as thermal management of microelectronics and batteries, design of plasmonic systems, mechanistic studies of catalysis, and unraveling intracellular processes. Upconverting nanoparticles (UCNPs) are lanthanide-doped inorganic probes that are popular luminescent thermometers, with advantages including well-understood temperature-dependent behavior, broadly tunable excitation and emission wavelengths, and exceptional thermal and chemical stability. Like other optical thermometry techniques, luminescence thermometry provides the desirable capability of remotely collecting the temperature-dependent signal from the far field. Conventional implementations of luminescence thermometry also share a major limitation of other optical thermometry techniques, namely, their diffraction limited spatial resolution. However, in contrast with other optical thermometry techniques, luminescence thermometry also creates an opportunity to leverage certain unique strategies for circumventing the diffraction limit.In this Account, we discuss our contributions to initiating or building on three major strategies for achieving UCNP thermometry beyond the diffraction limit. Some of these concepts originate from or have direct parallels in the realm of biological imaging, where optical imaging with spatial resolution below the diffraction limit has been a longstanding goal; conversely, others have no direct bioimaging analogy. Exciting an isolated single UCNP with a diffraction limited laser beam enables thermometry with subdiffraction limited spatial resolution governed by the UCNP size, although this approach is inherently restricted to measurements at a single spatial point. We begin by describing our efforts to extend single-UCNP measurements to smaller UCNP sizes and understand how their temperature-dependent emission can be influenced by external factors such as the excitation laser intensity or the surrounding optical environment, the latter of which is exemplified by an investigation of how single-UCNP emission is altered when the UCNPs are placed on various metallic substrates. Next, we show how the principles underlying single-UCNP thermometry can be expanded to sample multiple temperature points within a subdiffraction region by combining different UCNP compositions with spectrally orthogonal temperature-dependent luminescence. As a practical demonstration, we resolve a nearly 20 K temperature difference over a sub-110 nm distance originating from the steep temperature gradient near a laser-heated Ag nanodisk. Finally, we discuss our adaptation of UCNP-based stimulated emission depletion (STED) super-resolution imaging for super-resolution nanothermometry, combining temperature-dependent STED spectroscopy, self-assembled UCNP monolayer formation, and a detection scheme that enables practical scan times. STED nanothermometry can reveal a temperature gradient on a Joule-heated microstructure that is undetectable with analogous diffraction limited measurements, showcasing the power of this approach. We conclude with our perspective on the outlook for UCNP thermometry methods that circumvent the diffraction limit, highlighting both current research needs to further improve the measurement capabilities and strategies that could facilitate broader adoption of these emerging techniques.
Harrington et al. (Thu,) studied this question.