Persistent luminescence (PersL) imaging without real-time external excitation has been regarded as the next generation of autofluorescence-free and heating effect-free optical imaging technique. However, in order to acquire improved spatial resolution and deep penetration depth, developing new near-infrared (NIR) persistent phosphors with intense and long duration PersL over 1000 nm is still a challenging task. Herein, by utilizing the persistent energy transfer from Ce3+ to Er3+, we have successfully developed a series of garnet persistent phosphors of Gd3Al5-xGaxO12 (x=2.0, 2.5, 3.0, 3.5) doped with Ce3+, Cr3+ and Er3+ ions (GAGG:Ce-Cr-Er), which exhibit long yellow PersL ranging from 480 nm to 780 nm mainly due to the 5d-4f parity-allowed transition of Ce3+, and NIR PersL in the broad range from 1450 nm to 1670 nm due to the typical Er3+: 4I13/2→4I15/2 transition in garnets. Spectroscopic results of photoluminescence (PL), PersL, thermoluminescence (TL) and fluorescence/PersL decay curves of obtained garnet solid-solutions are discussed in detail, which suggest that GAGG:Ce-Cr-Er ganets with multi-wavelength PersL bands can be a potential candidate for longterm in-vivo optical imaging in the third biological window. Moreover, taking advantage of the Gd3+ host ion with seven unpaired electrons in its 4f shell, enhanced positive contrast for magnetic resonance imaging (MRI) also can be expected using this material as a T1-weighted agent. Thus, the GAGG:Ce-Cr-Er persistent phosphor in the form of nano-particles possesses the possibility as a dual-mode medical diagnosis platform featuring both the deep tissue penetration for in vivo bio-imaging and the high spatial resolution for MRI.
At the nanoscale, the ZnGa2O4 spinel doped with chromium (III) is an interesting material for in vivo optical imaging due to its bright red persistent luminescence after UV and visible excitation. Moreover its persistent luminescent properties can be improved with the incorporation of bismuth (III) as a co-dopant without any structure changes. The nanoparticles are synthesized by soft chemistry using microwave heating in aqueous media. These very small sized nanophosphors (around 10 nm) present interesting long lasting persistent luminescence after annealing at 1000°C and they can be excited both under UV and under visible LED excitation. In this work we try to understand the mechanisms of the persistent luminescent properties of such nanomaterials. Thermoluminescence is performed to investigate trapping and detrapping processes as well as trap distribution. The chromium local environment is studied by Electron Paramagnetic Resonance. 71Ga Nuclear Magnetic Resonance is used to get information on the gallium ions repartition (tetrahedral or octahedral site) in the structure. Comparison of optical properties versus local structure increases the understanding of the persistent luminescence mechanism and gives insights to the new modalities for their use as nanoprobes for in vivo imaging.
We investigated the blue excitable persistent luminescence properties in the Ce3+-doped garnet ceramics with the composition of Y3Al5-xGaxO12:Ce3+ (x=0, 1, 2, 3, 3.5, 4). The persistent luminescence was observed in the sample with x=3 and 3.5 by the blue excitation. In these materials, the energy gap between the lowest 5d1 excited level of Ce3+ and the conduction band is much closer compared with x=0, 1, 2 samples. As a result, the efficient electron transfer to the electron trap occurs through the conduction band by the blue excitation in the x=3 and 3.5 samples. The thermoluminescence (TL) was observed in all the samples by UV excitation and the TL peaks were shifted to lower energy with increasing Ga content. The decreases of the threshold energy of photoionization and the electron trap depth with increasing Ga content can be caused by lowering conduction band. Therefore, we demonstrated that the persistent luminescence properties, such as storagetable wavelength and persistent decay profile, are controlled by changing Ga content. We also discovered that the persistent luminescence intensity and duration time were improved by co-doping with metal ions.
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