We have studied the mechanisms of water-based quenching of the upconversion photoluminescence of upconverting nanophosphors (UCNPs) via luminescence decay measurements for a better understanding of the non-radiative deactivation pathways responsible for the relatively low upconversion luminescence efficiency in aqueous solutions. This included both upconversion luminescence measurements and the direct excitation of emissive energy states of Er(3+) and Yb(3+) dopants in NaYF4:Yb(3+),Er(3+) UCNPs by measuring the decays at 550 and 655 nm upon 380 nm excitation and at 980 nm upon 930 nm excitation, respectively. The luminescence intensities and decays were measured from both bare and silanized NaYF4:Yb(3+),Er(3+) and NaYF4:Yb(3+),Tm(3+) UCNPs in H2O and D2O. The measurements revealed up to 99.9% quenching of the upconversion photoluminescence intensity of both Er(3+) and Tm(3+) doped bare nanophosphors by water. Instead of the multiphonon relaxation of excited energy levels of the activators, the main mechanism of quenching was found to be the multiphonon deactivation of the Yb(3+) sensitizer ion caused by OH-vibrations on the surface of the nanophosphor. Due to the nonlinear nature of upconversion, the quenching of Yb(3+) has a higher order effect on the upconversion emission intensity with the efficient Yb-Yb energy migration in the ∼35 nm nanocrystals making the whole nanophosphor volume susceptible to surface quenching effects. The study underlines the need of efficient surface passivation for the use of UCNPs as labels in bioanalytical applications performed in aqueous solutions.

Photophysical studies of nonlinear lanthanide-doped photon upconverting nanoparticles (UCNPs) increasingly used in biophotonics and photovoltaics require absolute measurements of the excitation power density (P)-dependent upconversion luminescence (UCL) and luminescence quantum yields (Φ) for quantifying the material performance, UCL deactivation pathways, and possible enhancement factors. We present here the P-dependence of the UCL spectra, Φ, and slope factors of the different emission bands of representative 25 nm-sized oleate-capped β-NaYF:17% Yb, 3% Er UCNPs dispersed in toluene and as powder as well as Φ of 3 μm-sized upconversion particles (UCμP), all measured with a newly designed integrating sphere setup, enabling controlled variation of P over four orders of magnitude. This includes quantifying the influence of the beam shape on the measured Φ and comparison of experimental Φ with simulations utilizing the balancing power density model of the Andersson-Engels group and the simulated Φ of UCμP from the Berry group, underpinned by closely matching decay kinetics of our UC material. We obtained a maximum Φ of 10.5% for UCμP and a Φ of 0.6% and 2.1% for solid and dispersed UCNPs, respectively. Our results suggest an overestimation of the contribution of the purple and an underestimation of that of the red emission of β-NaYF:Yb,Er: microparticles by the simulations of the Berry group. Moreover, our measurements can be used as a guideline to the absolute determination of UCL and Φ.

Molecular photon upconversion luminescence was observed from an ion-associated complex of an erbium chelate of 2-thenoyltrifluoroacetone and a near-infrared-emitting cyanine dye in anhydrous solution at room temperature. In the complex erbium was sensitized by the organic antenna dye excited at 808 nm. The result was characteristic erbium emission at 510−565 nm with second-order dependence on the excitation power, suggesting a dye-sensitized energy transfer upconversion mechanism. Compared to inorganic upconverting nanoparticles, the organic molecular dye-sensitized complexes are expected to offer higher molar absorptivity, smaller well-defined size, and simpler addition of functional groups.

Synthetic hackmanites, Na8Al6Si6O24(Cl,S)2, showing efficient purple tenebrescence and blue/white persistent luminescence were studied using different spectroscopic techniques to obtain a quantified view on the storage and release of optical energy in these materials. The persistent luminescence emitter was identified as impurity Ti(3+) originating from the precursor materials used in the synthesis, and the energy storage for persistent luminescence was postulated to take place in oxygen vacancies within the aluminosilicate framework. Tenebrescence, on the other hand, was observed to function within the Na4(Cl,S) entities located in the cavities of the aluminosilicate framework. The mechanism of persistent luminescence and tenebrescence in hackmanite is presented for the first time.

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The mechanism for red upconversion luminescence of Yb–Er codoped materials is not generally agreed on in the literature. Both two-photon and three-photon processes have been suggested as the main path for red upconversion emission. We have studied β-NaYF4:Yb3+,Er3+ nanoparticles in H2O and D2O, and we propose that the nanoparticle environment is a major factor in the selection of the preferred red upconversion excitation pathway. In H2O, efficient multiphonon relaxation (MPR) promotes the two-photon mechanism through green emitting states, while, in D2O, MPR is less effective and the three-photon path involving back energy transfer to Yb3+ is the dominant mechanism. For the green upconversion emission, our results suggest the common two-photon path through the 4F9/2 energy state in both H2O and D2O.

The luminescence intensity ratio (LIR) of the green emissions of the near-infrared excited NaYF :Yb ,Er nanocrystals is a promising method for temperature sensing. Here, the influence of excitation power density, excitation pulse length, excitation wavelength, silica shell, and solvent on the LIR and its temperature response is reported. The primary objective is to study the LIR mechanism and the impact of measurement and environmental parameters on the calibration and precision of the LIR. The LIR value is demonstrated to be unaffected by the excitation intensity in the studied range. This result is essential, considering the application feasibility of the LIR method as temperature sensor, where the effective excitation power density depends on the sample matrix and the distance excitation light travels in the sample. The pulsed excitation, however, results in an increase in the LIR value upon short pulse width. Silanization of bare nanocrystals has no effect on the LIR values, but the local warming of H O samples under laser exposure results in slightly increased LIR values compared to other solvents; D O, oleic acid, and dimethyl sulfoxide. The thermal quenching of luminescence lifetimes of Er emission is proved to be too weak for sensing applications.

The sinusoidal modulation of excitation intensity and phase-sensitive detection of emission is ideally suitable for the accurate determination of the lifetime and intensity of lanthanide luminescence. In this work we elaborate on the general mathematical and instrumental techniques of the frequency-domain (FD) measurements in the low-frequency domain below 100 kHz. A modular FD luminometer is constructed by using a UV-LED as the excitation source, proper light filters in the excitation and emission paths, a photomultiplier with a fast preamplifier, and a conventional dual-phase lock-in amplifier. Starting from the set of linear differential equations governing the excited-state processes of the lanthanide chelates, an equation linking the luminescence intensity to the general form of the excitation modulation was derived. Application to the sinusoidal modulation in the Euler's exponential form gives the expression for the in-phase and out-of-phase signals of a dual-phase lock-in amplifier. It is shown that by using a relatively large number of logarithmically equidistant modulation frequencies it is possible to use the Kramers-Kronig relation for checking the compatibility of the out-of-phase and in-phase signals. As an example, the emission from two different europium(III) chelates were measured by using 200 modulation frequencies between 10 Hz and 100 kHz. In addition to the conventional transition between (5)D(0) and (7)F(2) levels emitting at 615 nm, also the emission from the transition between (5)D(1) and (7)F(1) levels at ca. 540 nm was measured. The latter emission was also measured at different temperatures, yielding the energy difference between the (5)D(1) and (5)D(0) levels. The relatively large number of modulation frequencies allows also an accurate determination of lifetimes and corresponding amplitudes by using an appropriate nonlinear regression method. Comparison of the time-domain and frequency-domain methods shows that the weighting of data is different and both methods have application areas of their own.