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Lanthanide (Ln3+)-doped upconversion (UC) nanocrystals have drawn tremendous attention because of their intriguing optical properties. Currently, it is highly desired but remains challenging to achieve efficient multiphoton UC emissions. Herein, we report the controlled synthesis of a new class of UC nanocrystals based on Cs2NaYF6:Yb/Tm nanoplatelets (NPs), which can effectively convert the 980 nm light to five-photon and four-photon UC emissions of Tm3+ without the fabrication of a complicated core/multishell structure required in traditional nanocrystals. Particularly, the as-prepared Cs2NaYF6:Yb/Tm NPs exhibit a maximal UV-to-NIR emission intensity ratio of 1.2, which is the highest among Tm3+-doped core-only UC nanocrystals. We reveal that the enhanced multiphoton UC emissions may benefit from the confined energy migration of Ln3+ dopants in the unique two-dimensional-like structure of Cs2NaYF6 NPs. As such, intense red and green UC emissions of Eu3+ and Tb3+ can further be generated via the cascade sensitization of Tm3+ and Gd3+ in Cs2NaYF6:Yb/Tm/Gd/Eu and Cs2NaYF6:Yb/Tm/Gd/Tb NPs, respectively. These results validate the superiority of Cs2NaYF6 for the future design of efficient UC nanocrystals towards versatile applications.

Highly toxic Pb2+ poses a great threat to the health of human beings and ecosystems, urgently calling for an efficient Pb2+ detection method. Herein, we demonstrated a brand-new solid-state fluorescence Pb2+-sensing scheme based on a type of Pb2+-responsive borate glass powder that is able to precipitate CsPbBr3 nanocrystals on the glass surface upon grinding with Pb2+ sources, following a mechanically driven glass crystallization mechanism. Pb2+ sensing is achieved via the Pb2+ concentration-dependent green emission of CsPbBr3 as an indicator signal and independent red emission of Eu3+ as a reference signal. Under UV light irradiation, the obvious emissive color variation from red to green as Pb2+ concentration varies enables the intuitive Pb2+-sensing by naked eyes. With the aid of a spectrometer and smartphone, Pb2+ concentration can be quantitatively determined with the detection limit as low as ∼70 ppm and ∼400 ppm, respectively. The semi-quantitative Pb2+ detection is also possible by comparing the emissive color with the calibrated color card. Hopefully, the proposed solid-state fluorescence Pb2+-sensing strategy with high selectivity can be used for portable and quick Pb2+ analysis in daily life.

Lanthanide (Ln3+)-doped NaREF4 (RE = rare earth) nanocrystals (NCs) are one of the most widely studied upconversion and downshifting luminescent nanoprobes. However, the size and optical performance of the Ln3+-doped NaREF4 NCs produced by the available lab-scale synthesis may vary from batch to batch, which inevitably limits their practical bioapplications. Herein, we report the synthesis of uniform Ln3+-doped NaREF4 NCs via a facile solid-liquid-thermal-decomposition (SLTD) method by directly employing NaHF2 powder as a fluoride and sodium precursor. The proposed SLTD strategy is easy to perform, time-saving and cost-effective, making it ideal for scale-up syntheses. Particularly, over 63 g of β-NaGdF4:Yb,Er@NaYF4 core/shell NCs with narrow size variation (<7%) were synthesized via a one-pot reaction. By virtue of their superior upconversion and downshifting luminescence, we employed the synthesized core/shell nanoprobes for the in vitro detection of prostate-specific antigen with a limit of detection down to 1.8 ng mL-1, and for in vivo near-infrared imaging with a high signal-to-noise ratio of 12. These findings may pave the way for the commercialization of Ln3+-doped nanoprobes in bioassay kits for versatile clinical applications.

Persistent luminescence nanoparticles (PLNPs) have shown great promise in the field of biomedicine, but are currently limited by the challenge in the synthesis of high-quality PLNPs with bright persistent luminescence and a long afterglow time. Herein, we report a facile strategy for the synthesis of monodisperse, rechargeable and LED-activated ZnGa 2 O 4  : Cr 3+ near-infrared (NIR) PLNPs based on a modified solvothermal liquid-solid-solution method. The as-synthesized PLNPs are not only flexible for bioconjugation, but could also circumvent the limitation of the weak persistent luminescence and short afterglow time that most PLNPs confronted owing to their rechargeable capability. It was unraveled that both thermal activation and quantum tunneling mechanisms contributed to the afterglow decay of the PLNPs, and the quantum tunneling was found to dictate the LED-activated afterglow intensity and lasting time. Furthermore, by utilizing the superior excitation-free persistent luminescence, we demonstrated for the first time the application of biotinylated ZnGa 2 O 4  : Cr 3+ PLNPs as background-free luminescent nano-bioprobes for sensitive and specific detection of avidin in a heterogeneous assay with a limit of detection down to ∼150 pM, thus revealing the great potential of these NIR PLNPs in ultrasensitive biodetection and bioimaging.

Lanthanide (Ln 3+ )-doped upconversion nanoparticles (UCNPs) have attracted tremendous interest owing to their potential bioapplications. However, the intrinsic photophysics responsible for upconversion (UC) especially the cooperative sensitization UC (CSU) in colloidal Ln 3+ -doped UCNPs has remained untouched so far. Herein, we report a unique strategy for the synthesis of high-quality LiYbF 4 :Ln 3+ core-only and core/shell UCNPs with tunable particle sizes and shell thicknesses. Energy transfer UC from Er 3+ , Ho 3+ and Tm 3+ and CSU from Tb 3+ were comprehensively surveyed under 980 nm excitation. Through surface passivation, we achieved efficient non-cooperative sensitization UC with absolute UC quantum yields (QYs) of 3.36%, 0.69% and 0.81% for Er 3+ , Ho 3+ and Tm 3+ , respectively. Particularly, we for the first time quantitatively determined the CSU efficiency for Tb 3+ with an absolute QY of 0.0085% under excitation at a power density of 70 W cm -2 . By means of temperature-dependent steady-state and transient UC spectroscopy, we unraveled the dominant mechanisms of phonon-assisted cooperative energy transfer (T > 100 K) and sequential dimer ground-state absorption/excited-state absorption (T < 100 K) for the CSU process in LiYbF 4 :Tb 3+ UCNPs.

Persistent luminescence phosphors, which are capable of emitting light for a long time after ceasing excitation, have shown great promise in diverse areas as bioprobes, lighting and displays. Exploring new materials to realize efficient persistent luminescence is a goal of general concern. Herein, we report a novel persistent luminescence phosphor based on Eu(3+)-doped SnO2 nanoparticles (NPs). The afterglow decay behaviour, the trap depth distribution as well as the underlying mechanism for persistent luminescence of the NPs were comprehensively surveyed by means of thermoluminescence and temperature-dependent afterglow decay measurements. It was found that the thermal activation mechanism is responsible for the afterglow decay of the NPs with an inverse power-law exponent of 1.0 (or 1.7) in the temperature region below (or above) 220 K. In particular, the co-existence of uniform and exponential distributions in trap depths may result in such a unique afterglow decay behaviour. These results reveal the great potential of SnO2 NPs as an excellent host material for Eu(3+) doping for the generation of efficient persistent luminescence.

Sr2YF7, as an important matrix for trivalent lanthanide (Ln(3+)) ions to fabricate upconversion (UC) or downshifting (DS) phosphors, has been rarely reported. Herein, monodisperse and size-controllable tetragonal-phase Ln(3+)-doped Sr2YF7 nanoparticles (NPs) were synthesized via a facile thermal decomposition method. Upon excitation at 980 nm, UC luminescence properties of Sr2YF7:Ln(3+)/Yb(3+) (Ln = Tm, Er) NPs were systematically surveyed. Particularly, after coating an inert Sr2YF7 shell, the UC luminescence intensities of Sr2YF7:Tm(3+)/Yb(3+) and Sr2YF7:Er(3+)/Yb(3+) NPs were enhanced by ∼22 and 4 times, respectively. Furthermore, intense multicolor DS luminescence was also achieved in Ce(3+)/Tb(3+) or Eu(3+) doped Sr2YF7 NPs, with absolute quantum yields of 55.1% (Tb(3+)) and 11.2% (Eu(3+)). The luminescence lifetimes of (5)D4 (Tb(3+)) and (5)D0 (Eu(3+)) were determined to be 3.7 and 8.1 ms, respectively. By utilizing the long-lived luminescence of Ln(3+) in these Sr2YF7 NPs, we demonstrated their application as sensitive heterogeneous time-resolved photoluminescence bioprobes to detect the protein of avidin and the tumor marker of the carcinoembryonic antigen (CEA) with their limits of detection down to 40.6 and 94.9 pM, and thus reveal the great potential of these Sr2YF7:Ln(3+) nanoprobes in cancer diagnosis.