Aurélie Bessière

Controlling Electron Trap Depth To Enhance Optical Properties of Persistent Luminescence Nanoparticles for In Vivo Imaging

Focusing on the use of nanophosphors for in vivo imaging and diagnosis applications, we used thermally stimulated luminescence (TSL) measurements to study the influence of trivalent lanthanide Ln(3+) (Ln = Dy, Pr, Ce, Nd) electron traps on the optical properties of Mn(2+)-doped diopside-based persistent luminescence nanoparticles. This work reveals that Pr(3+) is the most suitable Ln(3+) electron trap in the diopside lattice, providing optimal trap depth for room temperature afterglow and resulting in the most intense luminescence decay curve after X-ray irradiation. This luminescence dependency toward the electron trap is maintained through additional doping with Eu(2+), allowing UV-light excitation, critical for bioimaging applications in living animals. We finally identify a novel composition (CaMgSi(2)O(6):Eu(2+),Mn(2+),Pr(3+)) for in vivo imaging, displaying a strong near-infrared afterglow centered on 685 nm, and present evidence that intravenous injection of such persistent luminescence nanoparticles in mice allows not only improved but highly sensitive detection through living tissues.

Red persistent luminescence in MgGa2O4?:?Cr3+; a new phosphor for in vivo imaging

A new red-emitting long-lasting phosphorescence (LLP) material useful as biomarker for small animal in vivo imaging is presented. X-ray irradiated MgGa2O4 : Cr3+ is shown to be a suitable persistent phosphor emitting in the range 650–770 nm. In vivo re-excitation of its persistent luminescence is also possible with 580 nm excitation. MgGa2O4 : Cr3+ has almost 44% cationic site inversion. Cr3+ ion occupies octahedral site resulting in a broad emission peaking at 707 nm corresponding to Cr3+ 2E(2G) → 4A2(4F) transition. LLP is most intense for the compound with nominal Mg deficiency which also has the highest cation inversion. It is proposed that structural defects occurring due to cation inversion are responsible for LLP.

Defects Identification and Effects of Annealing on Lu 2(1-x) Y 2x SiO 5 (LYSO) Single Crystals for Scintillation Application

The nature, properties and relative concentrations of electronic defects were investigated by Thermoluminescence (TL) in Lu2(1-x)Y2xSiO5 (LYSO) single crystals. Ce and Tb-doped single crystals, grown by the Czochralski technique (CZ), revealed similar traps in TL. LYSO:Ce single crystals were grown by the Floating-Zone technique (FZ) with increasing oxygen concentration in the growth atmosphere. TL intensity is strongly dependent on the oxygen content of the material, and oxygen vacancies are proven to be the main electronic defects in LYSO. The effects of oxidizing and reducing annealing post-treatment on these defects were investigated. While oxidizing treatments efficiently reduce the amount of electronic defects, reducing treatments increase the amount of existing traps. In a thermally assisted tunneling mechanism, the localization of oxygen vacancies around the dopant is discussed. They are shown to be in the close vicinity of the dopant, though not in first neighbor positions.

Improved scintillation time response in (Lu0.5Gd0.5)2O3 : Eu3+ compared with Lu2O3 : Eu3+ transparent ceramics

The scintillation properties of two sesquioxides ceramics Lu2O3 : Eu3+ and (Lu0.5Gd0.5)2O3 : Eu3+ were studied. Both ceramics present comparable transparency and light yield whereas (Lu0.5Gd0.5)2O3 : Eu3+ showed an order of magnitude reduced afterglow in the 3–300 ms range. A thorough study of the location and behaviour of Eu3+ dopant ions at C2 and S6 sites of Lu2O3 and (Lu0.5Gd0.5)2O3 structures was carried out with low-temperature selective excitation of Eu3+. This revealed that (i) at both C2 and S6 sites, Eu3+ 4f–4f lifetime is shorter in (Lu0.5Gd0.5)2O3 : Eu3+ than in Lu2O3 : Eu3+, (ii) the host matrix (Lu0.5Gd0.5)2O3 as compared with Lu2O3 favours the location of Eu3+ at C2 site. As decay times of Eu3+ in C2 and S6 sites are 1.0 ms and 3.8 ms, respectively, the preferred occupation of C2 in (Lu0.5Gd0.5)2O3 : Eu3+ implies a much shorter decay time for (Lu0.5Gd0.5)2O3 : Eu3+ in the 3–20 ms range. Reduction of afterglow in the 20–300 ms range is illustrated by thermally stimulated luminescence peaks presenting a highly reduced intensity for (Lu0.5Gd0.5)2O3 : Eu3+ compared with Lu2O3 : Eu3+ implying reduced charge trapping defects in (Lu0.5Gd0.5)2O3 : Eu3+ ceramics.

Order and disorder around Cr(3+) in chromium doped persistent luminescent AB2O4 spinels.

The X-ray absorption near edge structure (XANES) spectroscopy technique is used to better understand the charging and decharging processes of the persistent luminescence in the Cr(3+)doped AB2O4 spinels (A = Zn, Mg and B = Ga and Al) with low photon energy excitation by visible light. Cr K edge XANES spectra have been simulated for different near neighbour environments around the Cr(3+) recombination centres and compared with the experimental curve. In the Cr(3+):ZnGa2O4 compound, the Cr(3+) local structure corresponds mostly to that of a normal spinel (∼70%), while the rest comprises of a distorted octahedral environment arising from cationic site inversion and a contribution from chromium clustering. This local structure is considerably different in Cr(3+):MgGa2O4 and Cr(3+):ZnAl2O4, where, for both cases, chromium clustering represents the main contribution. The strong correlation between the intensity of persistent luminescence and the percentage of Cr in clusters leads us to infer that the presence of Cr clusters is responsible for the decrease of the intensity of the visible light induced persistent luminescence in the Cr(3+) doped AB2O4 spinels.

Location of trivalent lanthanide dopant energy levels in (Lu0.5Gd0.5)2O3

The location of Ln3+ dopant energy levels relative to bands in (Lu0.5Gd0.5)2O3 was studied. A several-steps analysis of XPS measurements on heavy lanthanides sesquioxides Ln2O3 (Ln = Gd, Tb, Dy, Er, Tm, Yb, Lu) and on Sc2O3 and Y2O3 reference materials were used to locate Ln3+ dopant ground state relative to the top of the valence band in (Lu0.5Gd0.5)2O3 within an error bar of ±0.4 eV. The agreement between XPS data and model was found improved relative to previous studies. When compared to XPS analysis, prediction based on optical absorption shows a slight underestimation attributed to the lack of precision in Ce4+ charge transfer band measurement.

High Efficiency of Lutetium Silicate Scintillators, Ce-Doped LPS and LYSO Crystals for Medical Applications

The paper presents two cerium doped lutetium silicate crystals: pyrosilicate Ce:Lu2Si2O7 (LPS) and Ce: Lu2(1-x)Y2xSiO5 (LYSO). These two crystals exhibit the expected requirements for gamma detection: high density and high atomic number, high scintillation light yield, good energy resolution and fast response. LPS and LYSO crystals doped with cerium were grown by the Czochralski process. The crystal growth parameters were studied and optimized. Development of scintillators requires good understanding of the scintillation process. The location within the forbidden band gap of the localized lanthanide energy levels is analyzed by time resolved spectroscopy and thermoluminescence studies.

Trap depth optimization to improve optical properties of diopside-based nanophosphors for medical imaging

Regarding its ability to circumvent the autofluorescence signal, persistent luminescence was recently shown to be a powerful tool for in vivo imaging and diagnosis applications in living animal. The concept was introduced with lanthanide-doped persistent luminescence nanoparticles (PLNP), from a lanthanide-doped silicate host Ca0.2Zn0.9Mg0.9Si2O6:Eu2+, Mn2+, Dy3+ emitting in the near-infrared window. In order to improve the behaviour of these probes in vivo and favour diagnosis applications, we showed that biodistribution could be controlled by varying the hydrodynamic diameter, but also the surface charges and functional groups. Stealth PLNP, with neutral surface charge obtained by polyethylene glycol (PEG) coating, can circulate for longer time inside the mice body before being uptaken by the reticulo-endothelial system. However, the main drawback of this first generation of PLNP was the inability to witness long-term monitoring, mainly due to the decay kinetic after several decades of minutes, unveiling the need to work on new materials with improved optical characteristics. We investigated a modified silicate host, diopside CaMgSi2O6, and increased its persistent luminescence properties by studying various Ln3+ dopants (for instance Ce, Pr, Nd, Tm, Ho). Such dopants create electron traps that control the long lasting phosphorescence (LLP). We showed that Pr3+ was the most suitable Ln3+ electron trap in diopside lattice, providing optimal trap depth, and resulting in the most intense luminescence decay curve after UV irradiation. A novel composition CaMgSi2O6:Eu2+,Mn2+,Pr3+ was obtained for in vivo imaging, displaying a strong near-infrared persistent luminescence centred on 685 nm, allowing improved and sensitive detection through living tissues.

Up-Conversion in Yb,Er-Doped Y2O3 Nanoparticles for Cell Imaging

Y2O3:19%Yb,1%Er nanoparticles were synthesized with the aim of imaging the luminescent cell. Coprecipitation and combustion synthesis were used to obtain particulate sizes ranging from 25 up to 140 nm. The powders showed predominant red upconversion and the emission efficiency is controlled by the particle size. A colloidal route was also followed and 2-5 nm-large agglomerated nanoparticles were obtained. In that case, the luminescence of Er3+ was only observed by direct excitation and no upconversion light has been detected on these very small particles.

Observation of reduced radiative recombination in low-well-number strain-balanced quantum well solar cells

Absolute electroluminescence and photoluminescence measurements were carried out on strain-balanced quantum well solar cells. Over a range of bias, a reduced radiative recombination in the wells was observed compared to a model assuming a constant quasi-Fermi level separation (QFLS) over the device thickness. This was interpreted as a QFLS suppression in the wells relative to the bulk of 18 and 5 meV, respectively, for the single and five well strain-balanced quantum well solar cells, consistent with previous results on strained single quantum well and double quantum well devices. The photoluminescence spectra at open-circuit voltage under illumination in the well agreed with the electroluminescence spectra in the light in contrast to some theoretical predictions. Generation of hot carriers in the wells could be the thermodynamically compensating phenomenon for the QFLS reduction.