Delayed tunneling of charges to deep traps in a ZnO impurity containing Cr3+ doped Zn2TiO4 inverse spinel.

Herein, the structural, optical and thermoluminescence properties of Cr doped Zn2TiO4 are explored extensively for a possible application in bioimaging. All the samples show prominent luminescence at wavelengths 712 and 716 nm, which correspond to Cr R and N2-lines, respectively. These R and N2 lines correspond to the presence of Cr3+ in undistorted and distorted sites. The excitation spectra of all the samples possess at least five different bands at 616, 440, 388, 330 and 283 nm. The persistent luminescence is observed upon excitation at all these wavelengths, suggesting the existence of both localized and delocalized mechanisms. The charges can be easily stored in deeper traps (trap depth > 1.0 eV) upon localized excitation with green and red light sources. However, upon excitation at wavelengths 254 and 365 nm, these traps were found empty when thermoluminescence glow curves were recorded immediately after excitation. Furthermore, it was observed that the trapping in these deeper traps through the delocalized band is possible when a delay in the thermoluminescence measurement is pursued. We attribute the possible reason for such delayed tunneling to the higher probability of retrapping than the recombination process.

UV-A,B,C Emitting Persistent Luminescent Materials.

The nearly dormant field of persistent luminescence has gained fresh impetus after the discovery of strontium aluminate persistent luminescence phosphor in 1996. Several efforts have been put in to prepare efficient, long decay, persistent luminescent materials which can be used for different applications. The most explored among all are the materials which emit in the visible wavelength region, 400-650 nm, of the electromagnetic spectrum. However, since 2014, the wavelength range is extended further above 650 nm for biological applications due to easily distinguishable signal between luminescent probe and the auto-fluorescence. Recently, UV-emitting persistent materials have gained interest among researchers' due to their possible application in information storage, phototherapy and photocatalysis. In the present review, we summarize these recent developments on the UV-emitting persistent luminescent materials to motivate young minds working in the field of luminescent materials.

Comparing the optical properties and thermal stability of green (TbPO4), yellow (DyPO4), and red (PrPO4) emitting single crystal samples.

Blue, green and red-emitting phosphors for near-UV/blue based phosphor blend converted white-light emitting devices have been investigated extensively over the past years. Herein, we present our results on the optical spectroscopy of single crystal samples of TbPO4, DyPO4 and PrPO4 exhibiting prominent emission at green (545 nm), yellow (574 nm) and red (616 nm) region of the electromagnetic spectrum, respectively. We study the temperature dependence of their emission spectra for excitations at 365 and 455 nm, to mimic experimental conditions for phosphor converted light emitting diodes, to show that their thermal quenching temperature is 730 K for TbPO4 (excitation 365 nm), 490 and 520 K for DyPO4 (excitation at 365 and 455 nm), and 540 K for PrPO4 (excitation 455 nm). The TbPO4 emission does not show any considerable blue/red shift at elevated temperatures, while DyPO4 emission is observed close to the center of CIE coordinate diagram. The PrPO4 sample possesses high color purity which shows slight yellow-shift at elevated temperatures. The ground state of Pr3+ and Tb3+ are found to be within the band gap suggesting that both are able to trap holes from the valence band as evinced from the thermoluminescence glow curve data which shows peak maxima at 422 and 437 K due to hole release from the Pr4+ and Tb4+, respectively. The result suggests that the samples have large potential for solid state lighting devices upon choice of an appropriate excitation wavelength.

Non-quenching photoluminescence emission up to at least 865 K upon near-UV excitation in a single crystal of orange-red emitting SmPO4.

The adjustment of photoluminescence emission spectrum and an enhancement in the thermal stability of red/orange-red emitting phosphors is an important issue for the whole lighting industry. Herein, we present our results on the luminescence spectroscopy of a single crystal sample of SmPO4 exhibiting a prominent orange-red emission at 597 nm, along with a charge-transfer absorption (O2- → Sm3+) around 200 nm. We study the temperature dependence of emission spectra in SmPO4 for excitations at 365 and 455 nm, to mimic experimental conditions for phosphor converted light emitting diodes, to show that the sample has a non-quenching photoluminescence emission up to at least 865 K for an excitation at 365 nm, and ∼865 K for an excitation at wavelength, 455 nm. The thermal stability of SmPO4 was found to be much higher than its structural analogue, EuPO4, which is also an orange-red emission phosphor, but possesses a thermal quenching temperature of 710 K (exc. 365 nm), and 735 K (exc. 455 nm). The extraordinary thermal stability of SmPO4 is a result of the energy transfer from deep defects to the Sm3+ ions at high temperatures. The color purity of SmPO4 (65%) was found to be slightly lower than the EuPO4 sample (70%), at room temperature. The results suggests that the rare earth orthophosphate, SmPO4, has a large potential for near-UV excited phosphor converted solid state lighting devices.

Extending the temperature sensing range using Eu3+ luminescence up to 865 K in a single crystal of EuPO4.

Temperature evaluation through the measurement of emission intensities (the intensity ratio method) requires two distinct bands, one of which is used as a reference, and the emission intensity of the other is monitored as a function of a change in temperature. Herein, we report the influence of the excitation wavelength and a coupling scheme between the lanthanoid and defect emission from the host lattice to extend the temperature sensing range by using a single crystal of europium(iii) phosphate. The temperature dependence of the emission intensity was studied for different excitation wavelengths: 365 (intraconfigurational 4f2 excitation), 338 (defect excitation), and 254 nm (O2- → Eu3+ charge-transfer excitation), in the temperature range 293-865 K. We determined the Boltzmann equilibrium among different coupling schemes using a linear regression model to infer that for excitation at a 338 nm wavelength, and evaluating the intensity ratio between defect emission and the Eu3+ 5D0,17FJ transitions, the temperature sensing range can be extended up to at least 865 K, with relative sensitivity in the range 0.33-1.94% K-1 (at 750 K). The results showed a resolution of <1 K with excellent reproducibility, suggesting that the thermometers can be used with high reliability.

Controlling disorder in the ZnGa2O4:Cr3+ persistent phosphor by Mg2+ substitution.

We have studied in this work the effect of increasing structural disorder on the persistent luminescence of a Cr3+ doped zinc gallate spinel. This disorder was introduced by progressive substitution of Zn2+ by Mg2+ ions, and was studied by photoluminescence, X-ray diffraction, extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES) and electron paramagnetic resonance (EPR) spectroscopy. It was found that increasing the Mg/Zn substitution decreases the number of Cr3+ in undistorted sites and increases the number of Cr3+ with neighbouring antisite defects and with neighbouring Cr3+ ions (referred to as Cr clusters), which in turn decreases the intensity of persistent luminescence. Both XANES and EPR spectra could be simulated by a linear combination of Cr3+ spectra with three types of Cr3+ environments. The increasing disorder was found to be correlated with a decrease of the average Cr-O bond length and a decrease of crystal field strength experienced by Cr3+ ions.

Interaction of Cr(3+) with valence and conduction bands in the long persistent phosphor ZnGa2O4:Cr(3+), studied by ENDOR spectroscopy.

Cr(3+)-doped zinc gallate ZnGa2O4 is a red-near infrared (IR) long persistent phosphor that can be excited by orange-red light, in the transparency window of living tissues. With this property, persistent luminescence nanoparticles were recently used for in vivo optical imaging of tumors in mice. In order to understand the origin of the excitability of persistent luminescence by visible light in this material, a Q-band ENDOR investigation of (71/69)Ga and (53)Cr nuclei was performed in ZnGa2O4:Cr(3+) to get information on the interaction of Cr(3+) with valence and conduction bands. The positive electron spin density at Ga nuclei revealed a dominant interaction of the (4)A2 ground state of Cr(3+) with the valence band, and a weaker interaction with the conduction band. The latter may occur only in the excited (2)E and (4)T2 states of Cr(3+). It is proposed that when these two interactions are present, pairs of electrons and holes can be generated from excited Cr(3+) in distorted sites undergoing local electric field produced by neighboring defects with opposite charges.

Exploring stable thermoluminescence signal in natural Barite (BaSO4) for retrospective dosimetry.

We explore the possible use of Barite (BaSO4) for radiation dosimetry and geochronology using thermoluminescence technique. Natural Barite with Mn as an impurity has a glow peak at 608K with a minimum detectable dose of 1.45±0.12mGy. This peak shows ~35% fading on 30 days of storage time and is photo-bleachable with excellent reproducibility on repeated read-out. The sensitivity changes with dose and evidence of athermal fading is also seen. We infer that the signal can be used for both retrospective dosimetry and geochronology of young deposits extending to 20ka.

The importance of inversion disorder in the visible light induced persistent luminescence in Cr³âº doped AB2O4 (A = Zn or Mg and B = Ga or Al).

Cr(3+) doped spinel compounds AB2O4 with A = Zn, Mg and B = Ga, Al exhibit a long, near infrared persistent luminescence when excited with UV or X-rays. In addition, the persistent luminescence of ZnGa2O4, and to a lesser extent MgGa2O4, can also be induced by visible light excitation via (4)A2→(4)T2 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 ZnGa2O4 and MgGa2O4. 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 occurs 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 ZnAl2O4, 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 ZnGa2O4 and MgGa2O4. These results highlight the importance of Cr(3+) ions with neighboring antisite defects in the mechanism of persistent luminescence exhibited by Cr(3+) doped AB2O4 spinel compounds.

The in vivo activation of persistent nanophosphors for optical imaging of vascularization, tumours and grafted cells.

Optical imaging for biological applications requires more sensitive tools. Near-infrared persistent luminescence nanoparticles enable highly sensitive in vivo optical detection and complete avoidance of tissue autofluorescence. However, the actual generation of persistent luminescence nanoparticles necessitates ex vivo activation before systemic administration, which prevents long-term imaging in living animals. Here, we introduce a new generation of optical nanoprobes, based on chromium-doped zinc gallate, whose persistent luminescence can be activated in vivo through living tissues using highly penetrating low-energy red photons. Surface functionalization of this photonic probe can be adjusted to favour multiple biomedical applications such as tumour targeting. Notably, we show that cells can endocytose these nanoparticles in vitro and that, after intravenous injection, we can track labelled cells in vivo and follow their biodistribution by a simple whole animal optical detection, opening new perspectives for cell therapy research and for a variety of diagnosis applications.