Progress in discovery and structural design of color conversion phosphors for LEDs

Owing to the unique mechanism of photoelectron storage and release, long persistent phosphorescence, also called long persistent luminescence or long lasting afterglow/phosphorescence, plays a pivotal role in the areas of spectroscopy, photochemistry, photonics and materials science. In recent years, more research has focused on the manipulation of the morphology, operational wavebands and persistent duration of long persistent phosphors (LPPs). These desired achievements stimulated the growing interest in designing bio-labels, photocatalysts, optical sensors, detectors and photonic devices. In this review, we present multidisciplinary research on synthetic methods, afterglow mechanisms, characterization techniques, materials system, and applications of LPPs. First, we introduce the recent developments in LPPs for the synthesis of nanoparticles from the aspects of particle sizes, monodispersity and homogeneity based on the urgent application of bio-imaging. In the later sections, we present the possible mechanisms, which involve the variation of trap distribution during the trapping and de-trapping process, complicated photo-ionization reaction of trap site levels and impurity centers together with their corresponding migration kinetics of carriers. Meanwhile, we emphasize the characterization techniques of defects, used to qualitatively or quantitatively describe the types, concentrations and depths of the traps. This review article also highlights the recent advances in suggested LPPs materials with a focus on the LPPs' hosts and optically active centers as well as their control, tuning and intrinsic links. We further discuss the classification of LPPs based on the different emission and excitation wavebands from the ultraviolet to the near-infrared region along with an overview of the activation mode of afterglow. Afterwards, we provide an exhibition of new products towards diverse application fields, including solar energy utilization, bio-imaging, diagnosis, and photocatalysts. Finally, we summarize the current achievements, discuss the problems and provide suggestions for potential future directions in the aforementioned parts.

Long persistent phosphors—from fundamentals to applications

Nowadays, phosphor converted white light-emitting diodes (pc-WLEDs) have been widely used in solid-state lighting and display areas due to their superior lifetime, efficiency, and reliability as well as significant reduction in power consumption. Phosphors are indispensable components of pc-WLED devices, and their luminescence properties determine the quality of WLED lighting and displays. In order to further achieve high luminous efficacy, chromatic stability, and color-rending properties in pc-WLEDs, much effort has been focused on improving current pc-WLED phosphors and developing novel pc-WLED phosphors recently. This review article concerns commonly used rare earth ion (Eu2+ and Ce3+) activated inorganic phosphors, highlighting the important effect of spectral tuning via local structural variations on improving the luminescence performance of phosphors. The main spectral tuning strategies are discussed in detail and summarized, including (1) doping level control; (2) cationic substitution; (3) anionic substitution; (4) cationic–anionic substitution; (5) the crystal-site engineering approach; (6) mixing of nanophases.

Recent progress in luminescence tuning of Ce3+ and Eu2+-activated phosphors for pc-WLEDs

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted considerable interest due to their superior physicochemical features, such as large anti-Stokes shifts, low autofluorescence background, low toxicity and high penetration depth, which make them extremely suitable for use as alternatives to conventional downshifting luminescence bioprobes like organic dyes and quantum dots for various biological applications. A fundamental understanding of the photophysics of lanthanide-doped UCNPs is of vital importance for discovering novel optical properties and exploring their new applications. In this review, we focus on the most recent advances in the development of lanthanide-doped UCNPs as potential luminescent nano-bioprobes by means of our customized lanthanide photophysics measurement platforms specially designed for upconversion luminescence, which covers from their fundamental photophysics to bioapplications, including electronic structures (energy levels and local site symmetry of emitters), excited-state dynamics, optical property designing, and their promising applications for in vitro biodetection of tumor markers. Some future prospects and efforts towards this rapidly growing field are also envisioned.

Lanthanide-doped upconversion nano-bioprobes: electronic structures, optical properties, and biodetection

Phosphor-converted white light-emitting diodes (pc-WLEDs) are efficient light sources used in lighting, high-tech displays, and electronic devices. One of the most significant challenges of pc-WLEDs is the thermal quenching, in which the phosphor suffers from emission loss with increasing temperature during high-power LED operation. Here, we report a blue-emitting Na3–2xSc2(PO4)3:xEu2+ phosphor (λem = 453 nm) that does not exhibit thermal quenching even up to 200 °C. This phenomenon of zero thermal quenching originates from the ability of the phosphor to compensate the emission losses and therefore sustain the luminescence with increasing temperature. The findings are explained by polymorphic modification and possible energy transfer from electron–hole pairs at the thermally activated defect levels to the Eu2+ 5d-band with increasing temperature. Our results could initiate the exploration of phosphors with zero thermal quenching for high-power LED applications. A blue-emitting phosphor without thermal quenching is reported. The emission losses at high temperatures are compensated by a counter mechanism, originating in energy transfer between electron–hole pairs and thermally activated defect levels.

A zero-thermal-quenching phosphor

Manganese-activated fluoride phosphors for high-efficacy warm white light-emitting diodes have been limited by low photoluminescence quantum yields. Here, Zhu et al. use an efficient cation exchange reaction to synthesize manganese phosphors with photoluminescence quantum yields as high as 98%.

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Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes

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 ZnGa2O4 : Cr3+ 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 ZnGa2O4 : Cr3+ 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.

Rechargeable and LED-activated ZnGa2O4 : Cr3+ near-infrared persistent luminescence nanoprobes for background-free biodetection

Trivalent lanthanide ions (Ln(3+))-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc(3+) with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu(3+) at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln(3+) NPs were synthesized via a facile thermal decomposition method. The biotinylated NaScF4:Er(3+)/Yb(3+) NPs were demonstrated for their applications as a heterogeneous UC luminescence bioprobe to detect avidin with a detection limit of 180 pM. After bioconjugation with amino-terminal fragment (ATF) of urokinase plasminogen activator (uPA), NaScF4:Ln(3+) NPs also exhibited specific recognition of cancer cells overexpressed with uPA receptor (uPAR, an important marker of tumor biology and metastasis), showing great potentials in tumor-targeted bioimaging.

Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection

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 Eu3+-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 Eu3+ doping for the generation of efficient persistent luminescence.

Persistent luminescence from Eu3+ in SnO2 nanoparticles

We report the successful incorporation of Er3+ ions into SnO2 nanocrystals via a solvothermal method, with a resulting Er3+ concentration of the order of 1019 cm−3. Upon excitation above the SnO2 bandgap at 300 nm, intense and well-resolved Er3+-related photoluminescence (PL) at 1.55 μm was observed at room temperature. The results of PL excitation and ultraviolet/visible diffuse reflectance spectra indicate that the excitation is a carrier-mediated process with an energy transfer from the SnO2 host to Er3+. For the above-gap excitation, only a single type of Er3+ luminescence center located at a centrosymmetric site was identified. The near-infrared luminescence dynamics and the weak PL thermal quenching of Er3+ were also revealed.

Jintao Kong

Papers

Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes

Rechargeable and LED-activated ZnGa2O4 : Cr3+ near-infrared persistent luminescence nanoprobes for background-free biodetection

Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection

Persistent luminescence from Eu3+ in SnO2 nanoparticles

Carrier-mediated 1.55 microm photoluminescence from single Er3+ center in SnO2 nanocrystals.