The importance of inversion disorder in the visible light induced persistent luminescence in Cr3+^{3+} doped AB2_2O4_4 (A = Zn or Mg and B = Ga or Al)

Cr$^{3+}$ doped spinel compounds AB$_2$O$_4$ with A=Zn, Mg and B=Ga, Al exhibit a long near infrared persistent luminescence when excited with UV or X-rays. In addition, persistent luminescence of ZnGa$_2$O$_4$ and to a lesser extent MgGa$_2$O$_4$, can also be induced by visible light excitation via $^4$A$_2$ $\rightarrow$ $^4$T$_2$ transition of Cr$^{3+}$, which makes these compounds suitable as biomarkers for in vivo optical imaging of small animals. We correlate this peculiar optical property with the presence of antisite defects, which are present in ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. By using X-ray absorption fine structure (XAFS) spectroscopy, associated with electron paramagnetic resonance (EPR) and optical emission spectroscopy, it is shown that an increase in antisite defects concentration results in a decrease in the Cr-O bond length and the octahedral crystal field energy. A part of the defects are in the close environment of Cr$^{3+}$ ions, as shown by the increasing strain broadening of EPR and XAFS peaks observed upon increasing antisite disorder. It appears that ZnAl$_2$O$_4$, which exhibits the largest crystal field splitting of Cr$^{3+}$ and the smallest antisite disorder, does not show considerable persistent luminescence upon visible light excitation as compared to ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. These results highlight the importance of Cr$^{3+}$ ions with neighboring antisite defects in the mechanism of persistent luminescence exhibited by Cr$^{3+}$ doped AB$_2$O$_4$ spinel compounds.Comment: 10 pages + supplementary (available on request

Order and disorder around Cr 3+ in chromium doped persistent luminescent AB 2 O 4 spinels

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Interplay between chromium content and lattice disorder on persistent luminescence of ZnGa2O4:Cr3+ for in vivo imaging

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Origin of the visible light induced persistent luminescence of Cr3+-doped zinc gallate

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Storage of Visible Light for Long-Lasting Phosphorescence in Chromium-Doped Zinc Gallate

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Storage of Visible Light for Long-Lasting Phosphorescence in Chromium-Doped Zinc Gallate

ZnGa₂O₄:Cr³⁺ presents near-infrared long-lasting phosphorescence (LLP) suitable for in vivo bioimaging. It is a bright LLP material showing a main thermally stimulated luminescence (TSL) peak around 318 K. The TSL peak can be excited virtually by all visible wavelengths from 1.8 eV (680 nm) via d–d excitation of Cr³⁺ to above ZnGa₂O₄ band gap (4.5 eV–275 nm). The mechanism of LLP induced by visible light excitation is entirely localized around Cr_N2 ion that is a Cr³⁺ ion with an antisite defect as first cationic neighbor. The charging process involves trapping of an electron–hole pair at antisite defects of opposite charges, one of them being first cationic neighbor to Cr_N2. We propose that the driving force for charge separation in the excited states of chromium is the local electric field created by the neighboring pair of antisite defects. The cluster of defects formed by Cr_N2 ion and the complementary antisite defects is therefore able to store visible light. This unique property enables repeated excitation of LLP through living tissues in ZnGa₂O₄:Cr³⁺ biomarkers used for in vivo imaging. Upon excitation of ZnGa₂O₄:Cr³⁺ above 3.1 eV, LLP efficiency is amplified by band-assistance because of the position of Cr³⁺⁴T₁ (⁴F) state inside ZnGa₂O₄ conduction band. Additional TSL peaks emitted by all types of Cr³⁺ including defect-free Cr_R then appear at low temperature, showing that shallower trapping at defects located far away from Cr³⁺ occurs through band excitation