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.

Lanthanide-doped vanadate thin films offer (i) a promising platform for luminescence-based noncontact temperature sensing; (ii) ratiometric/self-referencing absolute measurements; (iii) exceptional repeatability and reversibility for multirun uses and a long life cycle; (iv) 2% K(-1) maximum temperature sensitivity (among the highest recorded for inorganic nanothermometers); (v) a temperature resolution greater than 0.5 K; and (vi) the potential for high-resolution 2D temperature mapping.

The near-infrared luminescence of Ca6Ba(PO4)4O:Mn5+ is demonstrated and explained. When excited into the broad and strong absorption band that spans the 500–1000 nm spectral range, this phosphor provides an ultranarrow (FWHM = 5 nm) emission centered at 1140 nm that originates from a spin-forbidden 1E → 3A2 transition with a 37.5% internal quantum efficiency and an excited-state lifetime of about 350 μs. We derived the crystal field and Racah parameters and calculated the appropriate Tanabe–Sugano diagram for this phosphor. We found that 1E emission quenches due to the thermally-assisted cross-over with the 3T2 state and that the relatively high Debye temperature of 783 K of Ca6Ba(PO4)4O facilitates efficient emission. Since Ca6Ba(PO4)4O also provides efficient yellow emission of the Eu2+ dopant, we calculated and explained its electronic band structure, the partial and total density of states, effective Mulliken charges of all ions, elastic constants, Debye temperature, and vibrational spectra. Finally, we demonstrated the application of phosphor in a luminescence intensity ratio thermometry and obtained a relative sensitivity of 1.92%K−1 and a temperature resolution of 0.2 K in the range of physiological temperatures.

No abstract

No abstract

Cr3+-doped Mg2SiO4 orthorhombic nanoparticles are synthesized by a combustion method. The 3d3 electron configuration of the Cr3+ ion results in the deep-red emission from optical transitions between d–d orbitals. Two overlapping emissions from the Cr3+ spin-forbidden 2Eg→ 4A2g and the spin-allowed 4T2g→ 4A2g electronic transitions are influenced by the strong crystal field in Mg2SiO4 and, thus, are suitable for ratiometric luminescence thermometry. The temperature-induced changes in Cr3+-doped Mg2SiO4 emission are tested for use in luminescence thermometry from cryogenic to physiologically relevant temperatures (10–350 K) by three approaches: (a) temperature-induced changes of emission intensity; (b) temperature-dependent luminescence lifetime; and (c) temperature-induced changes of emission band position. The second approach offers applicable thermometry at cryogenic temperatures, starting from temperatures as low as 50 K, while all three approaches offer applicable thermometry at physiologically relevant temperatures with relative sensitivities of 0.7% K−1 for emission intensity, 0.8% K−1 for lifetime and 0.85% K−1 for band position at 310 K.

No abstract

No abstract