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

Unraveling the impact of different thermal quenching routes on the luminescence efficiency of the Y3Al5O12:Ce3+ phosphor for white light emitting diodes

Cerium doped yttrium aluminium garnet, Y3-zCezAl5O12, is the prototype material for solid-state white lighting and it still is an important white LED phosphor. However, fundamental understanding of the thermal quenching of luminescence, which leads to a pronounced reduction of the emission intensity under high-power light-emitting diode operation, remains to be obtained. Here we show, through a multitechnique approach based on photoluminescence, thermoluminescence and mode-selective vibrational excitation experiments that thermal quenching of luminescence in Y3-zCezAl5O12 is caused by a combined effect of thermal ionization, thermally activated concentration quenching, and thermally activated 5d → 4f crossover relaxation via electron-phonon coupling, and establish the general trends upon variation of the Ce3+ concentration and temperature. Thermal quenching below 600 K is primarily the result of concentration quenching and crossover relaxation, which can be suppressed by keeping the Ce3+ dopant concentration far below 0.7 mol%, whereas for temperatures above 600 K thermal ionization is the predominating quenching process. This new insight into the interplay between different thermal quenching processes provides design principles for optimizing the light emittance and colour stability of new phosphor materials used in white lighting devices characterized by certain operating temperatures. This journal i

Photoluminescence Properties and Fabrication of Red-Emitting LEDs based on Ca9Eu(VO4)(7) Phosphor

We study the photoluminescence properties of the red-emitting phosphor Ca9Eu(VO4)(7) and establish a strong red emission centered at 613 nm under excitation at 395 nm (near ultra violet light, near-UV light) due to the intra-configurational D-5(0) -> F-7(2) transition within the 4f(6) configuration of the Eu3+ ions. The intensity of the emitted light decreases with increasing temperature and at T = 470 K about 50% of the intensity of the emitted light at room temperature is lost. Five different red-LED prototypes were constructed by applying a mixture of Ca9Eu(VO4)(7) phosphor and silicone gel on the headers of near-UV LED chips. The prototypes showed a color output from violet for the lowest phosphor concentration (133 g phosphor /l silicone gel), reaching an almost pure red-light output for the highest phosphor concentration (670 g phosphor /l silicone gel). The luminous efficiency of optical radiation (LER) was found to decrease slightly with increasing applied current. For the highest phosphor concentration, the LER decreases from 238 lmW(-1) for 1 mA current supply to 235 lmW(-1) for 18 mA current supply. The external quantum efficiency decreased from 7.33% for the lowest phosphor containing LED prototype to 4.13% for the highest one. (C) The Author(s) 2019. Published by ECS

Weak thermal quenching of the luminescence in the Ca3Sc2Si3O12:Ce3+ garnet phosphor

We report results of the luminescence properties of the three garnet type phosphors Ce3+-doped Ca3Sc2Si3O12(CSSO:Ce3+), Sr3Y2Ge3O12(SYG:Ce3+) and Y3Al5O12(YAG:Ce3+), investigated using optical spectroscopy techniques and vacuum referred binding energy (VRBE) diagram analysis. By monitoring the temperature dependence of the luminescence decay time we establish an excellent, intrinsic, thermal stability of luminescence in CSSO:Ce3+, with a nearly constant decay time (≈60 ns) up to, at least, T = 860 K. In comparison, SYG:Ce3+and YAG:Ce3+exhibit a significant reduction of the luminescence decay time upon heating, starting at around T = 280 K and T = 550 K, respectively, suggesting a lower internal thermal stability of luminescence in these two garnet phosphors. These findings are supported by the energy separation between the Ce3+5d1level and the conduction band (CB) of the respective hosts, which are found at 1.36 eV (CSSO:Ce3+), 0.45 eV (SYG:Ce3+), and 1.17 eV (YAG:Ce3+), respectively, as predicted by their VRBE diagrams. The performance of CSSO:Ce3+was evaluated by applying the phosphor on a blue InGaN LED. The system shows a luminous efficacy of optical radiation of 243 lm W-1and a linear response with increasing applied voltage, suggesting it is a highly promising phosphor for future technological applications, particularly at high temperature operating environments

Band Gap Modulation in Zn₂TiO₄ Spinels for Efficient UV-A Persistent Luminescence

Spinels are important materials for an application in bioimaging. The key advantage with spinel-type hosts is the presence of antisite defects, which act as charge reservoirs for trapping electrons and holes at complementary defect sites. This makes them a host system similar to a molecular system. Herein, we present a systematic approach to modulating the band gap of an inverse Zn2TiO4 spinel. With a change in ZnO concentration, the absorption band at 375 nm diminishes and disappears at a ZnO:TiO2 concentration of 1.40:1.00. The band gap of the material is modified from 3.30 to 4.40 eV. The crystal structure of the sample does not change drastically as determined using X-ray diffraction and Rietveld refinement. The Zn2TiO4 emits in the UV-A region with a lifetime in the time domain of ‘ns’. The sample also shows persistent luminescence of at least 15 min upon excitation with 254 nm with prominent emission in the UV-A region (300–390 nm). The present results open a new avenue for the synthesis of spinel hosts where the band gap can be modified with ease. The UV emission thus observed is expected to find usage in interesting applications like photocatalysis, anti-counterfeiting, water disinfecting, etc

Green persistent luminescence excitable by multiple wavelengths in the CaSc2O4:Ce3+ phosphor co-doped with Mg2+

Calcium scandate (CaSc 2 O 4 ), when substituted with a small amount of the activator ion Ce 3+ to replace Ca 2+ , is a recently discovered green-emitting phosphor promising for solid-state lighting applications. The co-doping with aliovalent ions to compensate for the net positive charge, as induced by the Ce 3+ dopants, is a common approach to change the defect structure and tune the performance of the phosphor, but the underlying mechanisms are unclear. Here we investigate the effect of co-doping with charge-compensating Mg 2+ to substitute for Sc 3+ , using photoluminescence and thermoluminescence techniques. In comparison to the defect structure in Ce 3+ doped CaSc 2 O 4 , the co-doping with charge-compensating Mg 2+ leads to the formation of new traps. These traps are featured by activation energies in the range 0.58–0.64 eV, can be emptied at room temperature and show green long-lasting phosphorescence after excitation at 454, 340, and 254 nm, respectively. Analysis of the spectroscopic results in terms of a vacuum referred binding energy diagram allows us to reach at a plausible luminescence mechanism in {Ce 3+ /Ce 3+ Mg 2+ }-doped CaSc 2 O 4

Influence of Ce3+ Concentration on the Thermal Stability and Charge-Trapping Dynamics in the Green Emitting Phosphor CaSc2O4:Ce3+

The influence of the Ce3+ concentration on the excitation and emission characteristics, thermal stability, and charge-trapping-detrapping dynamics, of the green-emitting phosphor Ce3+ doped calcium scandium oxide (CaSc2O4) with very dilute Ce3+ substitutions (0.5, 1.0, and 1.5%), has been investigated using optical spectroscopy techniques. The diffuse reflectance and excitation spectra are found to exhibit a nonsystematic behavior with varying Ce3+ concentration, mainly linked to spectral band-overlap, whereas the emission spectra display only minor changes with varying Ce3+ concentration, suggesting that the local structural coordination of the Ce3+ dopants remains the same for different Ce3+ dopant levels. The major impact of Ce3+ concentration is seen on the thermal quenching temperature, which is found to be as high as T-50% approximate to 600 K for the most dilute Ce3+ doping (0.5%), followed by T-50% approximate to 530 K for 1.0% doping and T-50% approximate to 500 K for 1.5% doping, respectively. The materials are found to display a red-shift of the emitted light from 518 to 535 nm with increasing temperature from T = 80 K to T = 800 K, for all Ce3+ dopant levels. Thermoluminescence glow curves provide evidence for five charge-trapping defects, which are found to exhibit different charge-trapping dynamics for excitation into different 5d levels. It is argued that the three deeper traps can be filled by athermal tunneling of charges from the Ce3+ 5d(1) level, while the two shallower traps can only be filled when the charges move through the conduction band of the material

Dynamics of Charges in Superlong Blacklight-Emitting CaB2O4:Ce3+ Persistent Phosphor

The optical and persistent luminescence properties of CaB2O4:Ce3+ phosphor are presented. The optical emission for excitation in the 250-340 nm wavelength region is dominated by two bands at 365 and 460 nm. Lifetime measurements suggested that the 365 nm emission band is due to interconfigurational Ce3+ 5d -> 4f transitions. Upon excitation with a 254 nm UV lamp, a superlong persistent luminescence in the UVA1 region (340-400 nm, blacklight) was observed, lasting for at least 15 h, and with excellent reproducibility, which is perfectly suitable for phototherapy application. The initial-rise method was applied on the thermoluminescence glow curves to determine the trap distribution and trap depth. The results suggest that one distinct trap, with an activation energy of similar to 0.52 eV, was solely responsible for the persistent luminescence in the CaB2O4:Ce3+ phosphor. The other traps had a quasi-continuous distribution, with activation energies between 0.56 and 1.15 eV. The proposed persistent luminescence and the thermoluminescence mechanisms are elucidated using experimental parameters obtained from the optical and thermoluminescence results and the theoretically calculated electronic structure of the Ce3+ ion in CaB2O4. The lowest Ce3+ 5d(1) level was found to be similar to 0.97 eV below the conduction band, and the persistent luminescence/thermoluminescence emission was dominated by the radiative transitions between Ce3+ energy levels, 5d -> F-2(5/2),(7/2)