Judd–Ofelt theory is a cornerstone of lanthanides’ spectroscopy given that it describes 4fⁿ emissions and absorptions of lanthanide ions using only three intensity parameters. A self-referenced technique for computing Judd–Ofelt intensity parameters from the excitation spectra of Eu³⁺-activated luminescent materials is presented in this study along with an explanation of the parametrisation procedure and free user-friendly web application. It uses the integrated intensities of the ⁷F₀ → ⁵D₂, ⁷F₀ → ⁵D₄, and ⁷F₀ → ⁵L₆ transitions in the excitation spectrum for estimation and the integrated intensity of the ⁷F₀ → ⁵D₁ magnetic dipole transition for calibration. This approach facilitates an effortless derivation of the Ω₆ intensity parameter, which is challenging to compute precisely by Krupke’s parametrisation of the emission spectrum and, therefore, often omitted in published research papers. Compared to the parametrisation of absorption spectra, the described method is more accurate, can be applied to any material form, and requires a single excitation spectrum.

The figures of merit of luminescence intensity ratio (LIR) thermometry for Er³⁺ in 40 different crystals and glasses have been calculated and compared. For calculations, the relevant data has been collected from the literature while the missing data were derived from available absorption and emission spectra. The calculated parameters include Judd–Ofelt parameters, refractive indexes, Slater integrals, spin–orbit coupling parameters, reduced matrix elements (RMEs), energy differences between emitting levels used for LIR, absolute, and relative sensitivities. We found a slight variation of RMEs between hosts because of variations in values of Slater integrals and spin–orbit coupling parameters, and we calculated their average values over 40 hosts. The calculations showed that crystals perform better than glasses in Er³⁺-based thermometry, and we identified hosts that have large values of both absolute and relative sensitivity.

The emission of Er³⁺ provides three combinations of emission bands suitable for ratiometric luminescence thermometry. Two combinations utilize ratios of visible emissions (²H_11/2→⁴I_15/2 at 523 nm/ ⁴S_3/2→⁴I_15/2 at 542 nm and ⁴F_7/2→⁴I_15/2 at 485 nm/ ⁴S_3/2→⁴I_15/2 at 545 nm), while emissions from the third combination are located in near-infrared, e.g., in the first biological window (²H_11/2→⁴I_13/2 at 793 nm/ ⁴S_3/2→⁴I_13/2 at 840 nm). Herein, we aimed to compare thermometric performances of these three different ratiometric readouts on account of their relative sensitivities, resolutions, and repeatability of measurements. For this aim, we prepared Yb³⁺,Er³⁺:YF₃ nanopowders by oxide fluorination. The structure of the materials was confirmed by X-ray diffraction analysis and particle morphology was evaluated from FE-SEM measurements. Upconversion emission spectra were measured over the 293–473 K range upon excitation by 980 nm radiation. The obtained relative sensitivities on temperature for 523/542, 485/542, and 793/840 emission intensity ratios were 1.06 ± 0.02, 2.03 ± 0.23, and 0.98 ± 0.10%K⁻¹ with temperature resolutions of 0.3, 0.7, and 1.8 K, respectively. The study showed that the higher relative temperature sensitivity does not necessarily lead to the more precise temperature measurement and better resolution, since it may be compromised by a larger uncertainty in measurement of low-intensity emission bands.