Luminescence (nano)thermometry is an increasingly important field for remote temperature sensing with high spatial resolution. Most typically, ratiometric sensing of the luminescence emission intensities of two thermally coupled emissive states based on a Boltzmann equilibrium is used to detect the local temperature. Dependent on the temperature range and preferred spectral window, various choices for potential candidates appear possible. Despite extensive experimental research in the field, a universal theory covering the basics of luminescence thermometry is virtually nonexistent. In this manuscript, a general theoretical framework of single ion luminescent thermometers is presented that offers simple, user-friendly guidelines for both the choice of an appropriate emitter and respective embedding host material for optimum temperature sensing. The results show that the optimum performance (thermal response and sensitivity) around T 0 is realized for an energy gap ∆E 21 between thermally coupled levels between 2k B T 0 and 3.41k B T 0. Analysis of the temperature-dependent excited state kinetics shows that host lattices in which ∆E 21 can be bridged by one or two phonons are preferred over hosts in which higher order phonon processes are required. Such a framework is relevant for both a fundamental understanding of luminescent thermometers but also the targeted design of novel and superior luminescent (nano)thermometers.

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The delicate dependence of the photoluminescence properties of Eu2+ on the structure of the perovskite-analogue iodides CsMI3 (M = Mg, Ca, Sr) is discussed.

Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd3+ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd3+ almost unique among all lanthanides. Typically, emission from the two 4F3/2 crystal field levels is used for thermometry but the small ~100 cm−1 energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the 4F5/2 and 4F3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd3+-doped LaPO4 and LaPO4: x% Nd3+ (x = 2, 5, 10, 25, 100) nanocrystals serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd3+ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd3+ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd3+ concentrations, cross-relaxation processes enhance the decay rates of the 4F3/2 and 4F5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd3+ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the 4F5/2 and 4F3/2 spin-orbit levels of Nd3+ makes it possible to tailor the thermometric performance of Nd3+ to enable physiological temperature sensing.

on luminescence thermometry offers an alternative that is capable of measuring heat generation and diffusion on the microscopic scale. [3] Among the various choices of luminescent systems, [4-9] crystals doped with lanthanide (Ln 3+) ions represent a particularly promising class of luminescent thermometers, because their dimensions can be tuned from a few nanometers to several micrometers and their photoluminescence spectrum is sensitive to temperature. A characteristic feature of Ln 3+ ions is their rich energy level structure, which results in emission spectra with well-separated lines. Typically, the luminescence intensity ratio (LIR) between two of these emission lines is used as a sensitive measure for the temperature of the Ln 3+-doped crystal. After insertion of these ratiometric thermometers into a system of interest, remote operation simply involves excitation by light and detection of the luminescence with standard spectroscopic equipment. The performance of a ratiometric thermometer is determined by how sensitively the LIR reacts to temperature. In general, the performance at a given temperature (T) is quantified in terms of the relative sensitivity [10]

Lanthanide-doped luminescent nanoparticles are an appealing system for nanothermometry with biomedical applications due to their sensitivity, reliability and minimally invasive thermal sensing properties. Here, we propose four unique hybrid organic-inorganic materials prepared by combining β-NaGdF4 and PMOs (Periodic Mesoporous Organosilica) or mSiO2 (mesoporous silica). PMO/mSiO2 materials are excellent candidates for biological/biomedical applications as they show high biocompatibility with the human body. On the other hand, the β-NaGdF4 matrix is an excellent host for doping lanthanide ions, even at very low concentrations with yet very efficient luminescence properties. We propose a new type of Er 3+ -Yb 3+ upconversion luminescence nanothermometers operating both in the visible and near infrared regime. Both spectral ranges permit promising thermometry performance even in aqueous environment. It is additionally confirmed that these hybrid materials are non-toxic to cells, which makes them very promising candidates for real biomedical thermometry applications. In several of these materials the presence of additional voids leaves space for future theranostic or combined thermometry and drug delivery applications in the hybrid nanostructures.

Ratiometric luminescence thermometry with trivalent lanthanide ions and their 4fn energy levels is an emerging technique for non-invasive remote temperature sensing with high spatial and temporal resolution. Conventional ratiometric luminescence thermometry often relies on thermal coupling between two closely lying energy levels governed by Boltzmann’s law. Despite its simplicity, Boltzmann thermometry with two excited levels allows precise temperature sensing, but only within a limited temperature range. While low temperatures slow down the nonradiative transitions required to generate a measurable population in the higher excitation level, temperatures that are too high favour equalized populations of the two excited levels, at the expense of low relative thermal sensitivity. In this work, we extend the concept of Boltzmann thermometry to more than two excited levels and provide quantitative guidelines that link the choice of energy gaps between multiple excited states to the performance in different temperature windows. By this approach, it is possible to retain the high relative sensitivity and precision of the temperature measurement over a wide temperature range within the same system. We demonstrate this concept using YAl3(BO3)4 (YAB):Pr3+, Gd3+ with an excited 6PJ crystal field and spin-orbit split levels of Gd3+ in the UV range to avoid a thermal black body background even at the highest temperatures. This phosphor is easily excitable with inexpensive and powerful blue LEDs at 450 nm. Zero-background luminescence thermometry is realized by using blue-to-UV energy transfer upconversion with the Pr3+−Gd3+ couple upon excitation in the visible range. This method allows us to cover a temperature window between 30 and 800 K.