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 ⁴F_3/2 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 ⁴F_5/2 and ⁴F_3/2 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 ⁴F_3/2 and ⁴F_5/2 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 ⁴F_5/2 and ⁴F_3/2 spin-orbit levels of Nd³⁺ makes it possible to tailor the thermometric performance of Nd³⁺ to enable physiological temperature sensing.

A promising way to improve the performance of luminescent materials is to combine them with noble metal nanoparticles. Herein, a set of silver/europium-doped lanthanum orthophosphate (Ag/La_0.95Eu_0.05PO₄) nanostructures with different concentrations of silver nanoparticles were prepared and investigated. The presented overlap between the strongest europium (Eu³⁺) excitation line and the broad silver nanoparticle surface plasmon resonance makes the combination prospective for coupling. X-ray powder diffraction confirmed the monoclinic monazite structure. The transmission electron microscopy revealed particles with a rod-like shape and ~4 aspect ratio. Photoluminescence spectra show characteristic Eu³⁺ ion red emission. One of the requirements for an enhanced luminescence effect is the precise control of the distance between the noble metal nanoparticles and the emitter ion. The distance is indirectly varied throughout the change of Ag nanoparticle concentration in the La_0.95Eu_0.05PO₄ host. The emission intensity increases with the increase in Ag nanoparticles up to 0.6 mol %, after which the luminescence decreases due to the nanoparticles’ close packing and aggregation leading to the displacement of La_0.95Eu_0.05PO₄ from the vicinity of the metal particles and reabsorption of the emitted light. The emission intensity of La_0.95Eu_0.05PO₄ increases more than three times when the Eu³⁺ excitation is supported by the localized surface plasmon resonance in the Ag/La_0.95Eu_0.05PO₄ nanostructures.

The optical properties of Mn⁵⁺ ions, which are responsible for the intense green–turquoise–blue coloration of Mn⁵⁺-based pigments and the near-infrared emission of phosphors, are the focus of this article. Mn⁵⁺ ions enter crystalline matrices in four-fold coordinated positions and can maintain their 5+ valence state when crystalline hosts meet the conditions described in this work. Mn⁵⁺ ions have [Ar]3d² electronic configuration and always experience a strong crystal field due to a high electric charge; therefore, their lower electronic states have the ³A₂ < ¹E < ¹A₁ < ³T₂ < ³T₁ progression in energy. We present the properties of several Mn⁵⁺-based pigments and discuss the electronic transitions responsible for their coloration. Specifically, we show that the color is determined by the spin-allowed ³A₂ → ³T₁(³F) absorption, which extends across the orange–red–deep red spectral region and is strongly influenced by crystal field strength. The narrow-band emission Mn⁵⁺-activated near-infrared phosphors arise from the spin-forbidden ¹E → ³A₂ transition, whose energy is independent of the crystal field strength and determined by the nephelauxetic effect. We demonstrate the linear relationship between ¹E state energy and the nephelauxetic parameter β₁ using Racah parameter literature data for Mn⁵⁺ phosphors. Lastly, we address the recent applications of these Mn⁵⁺ phosphors in luminescence thermometry.