Sol-Gel Synthesis of CaTiO3:Pr3+ Red Phosphors: Tailoring the Synthetic Parameters for Luminescent and Afterglow Applications.
ABSTRACT: Two sol-gel synthetic routes for the preparation of CaTiO3:Pr3+ red emitting phosphors were compared, with the aim of producing nanostructured materials with tailored luminescence/afterglow properties. The effect of the synthetic parameters, such as the addition of a stabilizer and calcination temperature, on the structural, morphological, and optical properties was investigated. The desired perovskite phase was obtained at a calcination temperature of 800 °C or higher. Although the use of acetic acid as the chelating agent leads to micrometric particles with heterogeneous composition, the presence of hydroxypropylcellulose (HPC) results in smaller, less aggregated particles as well as in a high phase purity. At the highest HPC content, surface Ca-rich impurities were detected, although no segregated Ca-rich phases were detectable by X-ray powder diffraction analyses. Luminescence properties were found to be positively related to the phase purity of the oxide, with the highest quantum yields at temperatures equal to or higher than 1000 °C. On the contrary, persistent luminescence properties were highest at intermediate calcination temperatures and for samples synthesized with acetic acid. Overall, a notable role of oxygen vacancies resulting from local Ca excess was observed, acting as trap levels promoting longer relaxation pathways. Thanks to the small-sized particles and best steady-state luminescent properties due to a substantial decrease of lattice defects, the HPC synthesis is a promising strategy for light-emitting diode applications. On the other hand, the acetic acid synthesis promoted a higher defect density, which is required for an efficient yield of light emission in the long time range and is thus more suitable for afterglow applications.
Project description:Mn4+-activated phosphors are emerging as a novel class of deep red/near-infrared emitting persistent luminescence materials for medical imaging as a promising alternative to Cr3+-doped nanomaterials. Currently, it remains a challenge to improve the afterglow and photoluminescence properties of these phosphors through a traditional high-temperature solid-state reaction method in air. Herein we propose a charge compensation strategy for enhancing the photoluminescence and afterglow performance of Mn4+-activated LaAlO? phosphors. LaAlO?:Mn4+ (LAO:Mn4+) was synthesized by high-temperature solid-state reaction in air. The charge compensation strategies for LaAlO?:Mn4+ phosphors were systematically discussed. Interestingly, Cl-/Na?/Ca2+/Sr2+/Ba2+/Ge4+ co-dopants were all found to be beneficial for enhancing LaAlO?:Mn4+ luminescence and afterglow intensity. This strategy shows great promise and opens up new avenues for the exploration of more promising near-infrared emitting long persistent phosphors for medical imaging.
Project description:Near-infrared (NIR) persistent phosphor ZnGa2O4:Cr3+ (ZGC) has unique deep-tissue rechargeable afterglow properties. However, the current synthesis leads to agglomerated products with irregular morphologies and wide size distributions. Herein, we report on in vivo rechargeable mesoporous SiO2/ZnGa2O4:Cr3+ (mZGC) afterglow NIR-emitting nanocomposites that are made by a simple, one-step mesoporous template method. At less than 600 °C, pores in mesoporous silica nanoparticles (MSNs) act as nanoreactors to generate in situ ZnGa2O4:Cr3+ NIR-persistent phosphors. The as-synthesized mZGC preserves defined size, morphology, and mesoporous nanostructure of the MSNs. The persistent luminescence of the as-synthesized mZGC is recharged in a simulated deep-tissue environment (e.g., ?8 mm pork slab) in vitro by using red light (620 nm). Moreover, mZGC can be repeatedly activated in vivo for persistent luminescence imaging in a live mouse model by using white LED as a light source. Our concept of utilizing mesoporous silica as nanoreactor to fabricate ZGC PL nanoparticles with controllable morphology and preserved porous nanostructure paves a new way to the development and the wide application of deep tissue rechargeable ZGC in photonics and biophotonics.
Project description:Phosphors emitting visible and near-infrared persistent luminescence have been explored extensively owing to their unusual properties and commercial interest in their applications such as glow-in-the-dark paints, optical information storage, and in vivo bioimaging. However, no persistent phosphor that features emissions in the ultraviolet C range (200-280?nm) has been known to exist so far. Here, we demonstrate a strategy for creating a new generation of persistent phosphor that exhibits strong ultraviolet C emission with an initial power density over 10 milliwatts per square meter and an afterglow of more than 2?h. Experimental characterizations coupled with first-principles calculations have revealed that structural defects associated with oxygen introduction-induced anion vacancies in fluoride elpasolite can function as electron traps, which capture and store a large number of electrons triggered by X-ray irradiation. Notably, we show that the ultraviolet C afterglow intensity of the yielded phosphor is sufficiently strong for sterilization. Our discovery of this ultraviolet C afterglow opens up new avenues for research on persistent phosphors, and it offers new perspectives on their applications in terms of sterilization, disinfection, drug release, cancer treatment, anti-counterfeiting, and beyond.
Project description:Luminescent metal-organic frameworks (MOFs) have received much attention due to their wide structural tunability and potential application in light-emitting diodes, biological imaging and chemical sensors. However, successful examples of long-persistent afterglow MOFs are still quite limited to date. In this work, we report that two types of Zn-terephthalate (TPA) MOFs (namely [Zn(TPA)(DMF)] (1-DMF) and MOF-5) could exhibit an obvious room-temperature afterglow emission with a time-resolved luminescence lifetime as high as 0.47 seconds. The phosphorescence-based afterglow was also highly sensitive to the temperature, and the reversible emission intensity could be recycled under high/low temperatures. Moreover, both 1-DMF and MOF-5 showed highly tunable afterglow phosphorescence colors (from cyan to yellow and from green to red, respectively) upon treatment with pyridine solution. The fluorescence/phosphorescence emission color of MOF-5 can be reversibly switched due to the addition and removal of a pyridine guest to and from the host nanochannel, as shown in both experimental and computational studies. Therefore, this work not only shows a facile method to develop MOF-based long-afterglow materials at room temperature, but also presents a strategy to tune their phosphorescence in a wide range based on host-guest interactions.
Project description:There is a significant drive to identify alternative materials that exhibit room temperature phosphorescence for technologies including bio-imaging, photodynamic therapy and organic light-emitting diodes. Ideally, these materials should be non-toxic and cheap, and it will be possible to control their photoluminescent properties. This was achieved here by embedding carbon nanodots within crystalline particles of alkaline earth carbonates, sulphates and oxalates. The resultant nanocomposites are luminescent and exhibit a bright, sub-second lifetime afterglow. Importantly, the excited state lifetimes, and steady-state and afterglow colours can all be systematically controlled by varying the cations and anions in the host inorganic phase, due to the influence of the cation size and material density on emissive and non-emissive electronic transitions. This simple strategy provides a flexible route for generating materials with specific, phosphorescent properties and is an exciting alternative to approaches relying on the synthesis of custom-made luminescent organic molecules.
Project description:This article explains the behavior of afterglow luminescence using the trap bag concept, in which a constant phosphor dose contains a presumed bag with the ability to capture or release electrons through its opening. Luminescence is emitted as the bag releases the captured electrons. The electron-holding capacity is determined by the irradiation conditions, the width of the opening, and the electron activation; these factors are inherent properties of the long persistent luminescence (PLUM) dose and are affected by the thermal status. During the afterglow stage, higher temperatures may result in a wider opening and increased activation of electrons released from the bag, thus creating a higher light intensity and leading to the quicker exhaustion of the electrons within. In contrast, the opposite phenomenon will occur at lower temperatures. This article provides a detailed explanation of the trap bag concept at various thermal statuses and provides a method for delaying the afterglow peak profile through temperature change. Experimental tests were performed to confirm the proposed concept.
Project description:Tetravalent manganese doped phosphors are emerging as a new class of efficient near-infrared emitters for applications in a variety of areas, such as bioimaging and night-vision surveillance. Novel double perovskite-type La2MgGeO6:Mn4+ phosphors were successfully prepared using a microwave-assisted energy-saving solid state method. This simple technique involving the use of a microwave susceptor allows for a reduction of the preparation time compared to a conventional solid state reaction. The samples were investigated using powder X-ray diffraction, scanning electron microscopy, as well as energy-dispersive X-ray spectroscopy mapping, photoluminescence excitation/emission spectroscopy, persistent luminescence decay and temperature-dependent photoluminescence analysis. Substitution between isovalent Mn4+ and Ge4+ can be achieved without additional charge compensators in this germanate-based phosphor, which provides strong emission in the near-infrared spectral region, assigned to the characteristic transitions of tetravalent manganese ions. Additionally, the double perovskite-type germanate phosphor exhibits excellent luminescence thermal stability. Moreover, the spectroscopic properties, excitation wavelength-dependent and temperature-dependent persistent luminescence were studied. A series of thermoluminescence measurements were presented trying to give clear information on the charging process, afterglow behavior and the nature of the traps responsible for the persistent luminescence. The present investigation expands the range of available promising near-infrared emitting persistent phosphors for medical imaging.
Project description:Flexible 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized nanofibrillated cellulose (ONFC) films with long afterglow luminescence containing modified SrAl?O?: Eu2+, Dy3+ (SAOED) phosphors were fabricated by a template method. Tetraethyl orthosilicate (TEOS) and (3-aminopropyl) trimethoxy-silane (APTMS) were employed cooperatively to improve the water resistance and compatibility of the SAOED particles in the ONFC suspension. The structure and morphology after modification evidenced the formation of a superior SiO? layer and coarse amino-compounds on the surface of the phosphors. Homogeneous dispersions containing ONFC and the modified phosphors were prepared and the interface of composite films containing the amino-modified particles showed a more closely packed structure and had less voids at the interface between the cellulose and luminescent particles than that of silica-modified phosphors. The emission spectra for luminescent films showed a slight blue shift (3.2 nm) at around 512 nm. Such flexible films with good luminescence, thermal resistance, and mechanical properties can find applications in fields like luminous flexible equipment, night indication, and portable logo or labels.
Project description:Semiconducting polymer (SP)-based afterglow luminogens are showing increasing potential for in vivo imaging because of their long-life luminescence and the associated benefits (e.g., zero-autofluorescence background and high signal-to-noise ratio). However, such organic afterglow luminescence agents are still rare and their application is usually limited by their relatively low afterglow intensity and short afterglow duration. Herein, we report an aggregation-induced emission (AIE) dye-powered SP afterglow luminogen by leveraging on the unique characteristics of an AIE dye to circumvent the concentration-quenching effect, enhance afterglow intensity and prolong afterglow duration. The underlying working mechanism is investigated by a series of experiments and it is found that the AIE dye provides sufficient 1O2 to excite SPs and form massive amounts of high-energy intermediates, and then the SP intermediates emit photons that can activate the AIE dye to generate 1O2 and simultaneously trigger the energy transfer process between the SPs and AIE dye, resulting in a deep-red emission. It is this closed-loop of "photon-1O2-SP intermediates-photon" that provides the afterglow emission even after the cessation of the excitation light. The as-prepared luminogen shows good performance in in vivo tumour imaging. This study demonstrates the advantages of AIE-facilitated afterglow luminescence and discloses its mechanism, and hopefully it could inspire the development of other innovative designs for cancer theranostics.
Project description:Development of persistent luminescent materials has drawn continuous attention in recent years in view of their potential applications in the fields of security night-vision signage, in vivo bio-imaging and optical data storage. Currently, the normative evaluation of a new persistent luminescent material is focused on the light emission spectrum, the afterglow decay curve and the total duration time of the persistent luminescence. In this paper, we investigate the temperature dependent persistent luminescence in some well-known persistent phosphors and relate this to their thermoluminescence properties. The concept of the optimum working temperature is proposed as a new means for evaluating persistent phosphors. It is shown that there is a clear relation between the efficient temperature range of the afterglow output and the thermoluminescence glow curve. The experimental work is supported by simulations of thermoluminescence and afterglow characteristics. The concept of the optimum working temperature for persistent phosphors can be used as an evaluative criterion for applications in various working environments.