Quenching of Lanthanide Emission by Intervalence Charge Transfer in Crystals Containing Closed Shell Transition Metal Ions

The quenching of the luminescence originating from the excited states ³P₀ and ¹D₂ of Pr³⁺ and ⁵D₃ and ⁵D₄ of Tb³⁺ has been studied in oxide crystals containing closed shell transition metal ions, such as titanates, vanadates, niobates, and tantalates. It has been shown that the emission from these excited states can be quenched by an intervalence charge transfer mechanism. The temperature dependence of the emission intensities has allowed estimating indicative activation energies for the crossover to the intervalence charge transfer state. In the case of Tb³⁺, the quenching gives rise to relatively short decay times for the ⁵D₄ state.     

Calcination temperature optimization,energy transfer mechanism and fluorescence temperature dependence of KLa(MoO4)2:Eu3+ phosphors

The optimum calcination temperature for KLa(MoO₄)₂:Eu³⁺ phosphor was confirmed to be 1000 °C via checking the XRD patterns, SEM images and fluorescence spectra for the samples derived from solid state reaction. The energy transfer behavior between Eu³⁺ ions was studied. It was found that electric dipole–dipole interaction is responsible for the fluorescence quenching of ⁵D₂ and ⁵D₁ levels, but exchange interaction is in charge of ⁵D₀ fluorescence quenching. It was also observed that color coordinates of the studied phosphor can be tuned when the doping concentration is relatively low. The fluorescence thermal quenching process was investigated. It was found the thermal quenching followed well crossover model. Judd–Ofelt parameters of Eu³⁺ in KLa(MoO₄)₂ were obtained, and the optical transition properties were further discussed.     

Concentration influence on temperature-dependent luminescence properties of samarium substituted strontium tetraborate

The series of divalent samarium substituted strontium tetraborate (Sr_1?xSm_xB₄O₇) polycrystalline samples were prepared by the conventional solid-state reaction. The phase formation of the samples was investigated by X-ray powder diffraction measurements. The luminescence spectra and decay curves of the Sm²⁺ ions were measured. Temperature dependent Sm²⁺ luminescence properties were investigated. The f–d and ⁵D₁–⁷F_J transitions appeared at 350 K and increased with increase in the temperature while the intensity of ⁵D₀–⁷F_J transitions decreased. The emission spectra pointed out that Sm²⁺ occupies of C_2v or lower symmetry site. The photoluminescence decay times of strontium tetraborate doped with different concentrations of Sm²⁺ was investigated as a function of temperature in the range of 100–500 K. However, no obvious concentration quenching was observed.     

Synthesis and Sm/Sm doping effects on photoluminescence properties of Sr4Al14O25

Complete and partial samarium reduction was achieved under strong reducing atmosphere by solid-state and combustion synthesis of Sr_3.96Sm_0.04Al₁₄O₂₅. Dependence of different fluxing agents on the formation of various strontium aluminates was examined. The samples were investigated by X-ray powder diffraction, temperature dependent luminescence decay and photoluminescence measurements. Excitation with UV radiation resulted in sharp and well resolved emission lines of samarium ions. Distinct temperature behavior for Sm²⁺ and Sm³⁺ were detected in the range of 100-500 K. Estimated emission thermal quenching values (TQ_1/2) for divalent samarium were approximately 270 K while for trivalent state around 660 K. Measured luminescence decay values of Sm²⁺ are substantially lower than for Sm³⁺,≈1.7 and ≈2.7 ms, respectively. The spectral feature of Sm²⁺ emission spectrum indicates that dopant occupies low symmetry site in Sr₄Al₁₄O₂₅ compound.     

The effect of charge compensation by means of Na+ ions on the luminescence behavior of Sm3+-doped CaAl4O7 phosphor

Results of structural and spectroscopic measurements of Sm³⁺ doped calcium aluminates: Ca_1?xSm_xAl₄O₇ and Ca_1?2xSm_xNa_xAl₄O₇ (x=0.0005, 0.002, 0.01, 0.02, 0.03, 0.05) obtained by the modified Pechini method are presented. All samples yield intense orange–red emission under violet excitation (404.5 nm). Narrow bands corresponding to characteristic f–f intraconfigurational transition of Sm³⁺ in excitation and emission spectra were observed. The influences of the concentration of Sm³⁺ as well as charge compensation by co-doping with Na⁺ ions on the luminescent properties of the phosphor were investigated. Detailed analysis of the emission spectra of Sm³⁺ doped and Sm³⁺,Na⁺ co-doped CaAl₄O₇ powders proved that activator ions substitute Ca²⁺ in the host. Co-doping with Na⁺ ions enhanced greatly the intensity of the luminescence. Concentration dependencies of the intensity of luminescence and its decay kinetics proved the emission quenching at higher dopant contents due to cross-relaxation processes between Sm³⁺ ions. Fitting of the ⁴G_5/2 state fluorescence decay to the Inokuti–Hirayama model indicated dipole–dipole interaction as the dominant mechanism of the cross-relaxation processes.     

Fluorescence enhancement of oxide fluoride glass co-doped with TbF3 and SmF3

The fluorescence property of xTbF₃-BaF₂-AlF₃-GeO₂+ySmF₃ (x=0.01-40 mol%, y=0-5 wt%) glasses were investigated. The enhancement of Sm³⁺ fluorescence was recognized in the presence of Tb³⁺. Increasing Tb³⁺ content, the emission color changed from green to orange. When the intensity of fluorescence at 540 nm originated from Tb³⁺ is compared with that at 600 nm originated from Sm³⁺, the information about the concentration quenching of Tb³⁺ and Sm³⁺ was obtained. From these results, rare earth ions were dispersed identically in the glasses. After heating to 673 K or cooling to 77 K, the emission color of 20TbF₃-20BaF₂-10AlF₃-50GeO₂/mol%+0.05 wt% SmF₃ glass was reversibly changed from orange to green. In addition, while the emission from 10TbF₃-20BaF₂-10AlF₃-60GeO₂+0.01 wt% SmF₃ glass was green, its crystallized sample, prepared by annealing at 1073 K, exhibited an orange emission due to Sm³⁺ at room temperature.     

Synthesis and photoluminescence properties of Sm-doped CaWO4 nanoparticles

The Sm³⁺-doped CaWO₄ nanoparticles were synthesized by hydrothermal method. The room temperature photoluminescence (PL) spectra of Sm³⁺-doped CaWO₄ nanoparticles doped with different Sm³⁺ concentrations under 405 nm excitation have been investigated. The PL spectra showed four strong emission peaks at 460, 571, 609, and 653 nm. The first emission peak at 460 nm could be due to a structural defect of the lattice, an oxygen-deficient WO₃ complex. The other three emissions at 571, 609, and 653 nm were due to the f-f forbidden transitions of the 4f electrons of Sm³⁺, corresponding to ⁴G_5/2→⁶H_5/2 (571 nm), ⁶H_7/2 (609 nm), and ⁶H_9/2 (653 nm), respectively. In addition, the optimum Sm³⁺ concentration in CaWO₄ nanoparticles for optical emission was determined to be 1.0%. The Sm³⁺⁴G_5/2→⁶H_7/2 (609 nm) emission intensity of Sm³⁺-doped CaWO₄ nanoparticles significantly increased with the increase of Sm³⁺ concentration, and showed a maximum when Sm³⁺ doping content was 1.0%. If Sm³⁺ concentration continued to increase, namely more than 1.0%, the Sm³⁺⁴G_5/2→⁶H_7/2 emission intensity would decrease. The present materials might be a promising phosphor for white-light LED applications.     

Luminescent properties of a new green emitting Eu doped CaZrSi2O7 phosphor for WLED applications

CaZrSi₂O₇ (CZS), a modification of the thortveitite family, was prepared as a polycrystalline powder material by the conventional solid-state reaction method. Structural, thermal and photoluminescence (PL) properties of the prepared material were investigated in order to evaluate its potentiality. XRD patterns confirm the monoclinic phase of CaZrSi₂O₇: Eu²⁺ phosphors.. Emissions arising from transitions between the 5d and 4f orbital gaps of Eu²⁺ are manifested in the broadband excitation and emission spectra with major peaks at 363 and 512 nm, respectively. The excitation wavelength matches well with that of the emission of the ultraviolet-light emitting diode (UV-LED). Concentration quenching occurs when the Eu²⁺ concentration is beyond 0.05 and the dipole-dipole interaction was the reason for the corresponding quenching mechanism. The temperature dependence of emission intensity of CZS: Eu²⁺ phosphor was investigated and it showed better thermal stability than the standard YAG: Ce³⁺ phosphor.     

Analysis of Energy Transfer and Concentration Quenching in Sm3+-Activated Borate GdB3O6 Phosphors by Means of Fluorescence Dynamics

This article reports on the optical properties of Sm³⁺-activated GdB₃O₆ phosphors based on the measurement of their photoluminescence spectra and luminescence decay curves. Energy transfer from Gd³⁺ to Sm³⁺ and the concentration quenching of the Sm³⁺ ion emission are investigated. From the photoluminescence spectra and decay curves, the energy transfer from Gd³⁺ to Sm³⁺ is confirmed. The concentration quenching of the Sm³⁺ ion emission can be ascribed to resonant cross-relaxation. The interaction between the Sm³⁺ ions is derived of the electric dipole–dipole type through fitting the data with the Inokuti-Hirayama model. The critical distances and energy transfer microparameter for the transfer processes are given. The decay curves of Sm³⁺⁴G_5/2 level exhibiting a buildup and decay process also confirm the energy transfer from Gd³⁺ to Sm³⁺ and between Sm³⁺ ions.     

On the luminescent behaviour of europium in yttrium oxide and yttrium vanadate hosts

Europium-doped Y₂O₃ and YVO₄ were excited by ultraviolet and 10 kV electrons to give the red emission of Eu³⁺. Increase in the fluorescence output with temperature under uv excitation results from an increased absorption and a more efficient energy transfer to the Eu³⁺ ions from charge-transfer states involving the Y-O and V-O componensts of the lattices. The absence of thermal quenching of fluorescence for (Y₂O₃Eu) is attributed to the high energy of its charge-transfer states which forbids the⁵ D ₀ state to come into thermal contact with them. Complete quenching would occur above 2000 K as predicted from an estimated activation energy of 24 417 cm^–1. Quenching of cathodoluminescence of (YVO₄Eu) commences at 150 K due to the lower energy of its charge-transfer states. The experimentally-deduced temperature for complete quenching of cathodoluminescence for (YVO₄Eu) is lower than that predicted from an estimated thermal activation energy of 14 217 cm^–1; the difference being attributed to localized heating effects induced by electron bombardment. It is suggested that europium ions do not take part in thermoluminescence processes. Electron-hole recombinations occur at host sites to give the observed glow peaks which have been ascribed to traps produced by lattice defects and uncontrollable impurities in the undoped hosts.     

Ionic liquid-assisted hydrothermal synthesis of dendrite-like NaY(MoO4)2:Tb phosphor

Micro-sized NaY(MoO₄)₂:Tb³⁺ phosphors with dendritic morphology was synthesized by a ionic liquid-assisted hydrothermal process. X-ray diffraction (XRD) indicated that the as-prepared product is pure tetragonal phase of NaY(MoO₄)₂. Field emission scanning electron microscopy (FE-SEM) images showed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors have dendritic morphology. The photoluminescent (PL) spectra displayed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors show a stronger green emission with main emission wavelength 545 nm corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, and the optimal Tb³⁺ doping concentration for obtaining maximum emission intensity was confirmed to be 10 mol%. Based on Van Uitert's and Dexter's models the electric dipole–dipole (D–D) interaction was confirmed to be responsible for the concentration quenching of ⁵D₄ fluorescence of Tb³⁺ in the NaY(MoO₄)₂:Tb³⁺ phosphors. The intrinsic radiative transition lifetime of ⁵D₄ level is found to be 0.703 ms.     

Spectral hole burning and fluorescence in femtosecond laser induced Sm-doped glasses

The femtosecond laser was used to irradiate sol-gel derived Sm³⁺-doped Al₂O₃-SiO₂ glasses, in which the Sm³⁺ was reduced into Sm²⁺ ions. The fluorescence line narrowing was applied to investigate the coordination sphere of the Sm²⁺ ion. The spectral hole burning was performed on ⁷F₀→⁵D₀ transition of the Sm²⁺. The depth and width of the burnt holes were ∼27% and ∼4 cm⁻¹ FWHM at 7 K, respectively. Hole spectra were stable up to room temperature. The hole-burning efficiency was superior to that of Sm²⁺ in H₂ treated glasses and comparable to that in X-ray in terms of hole-burning dynamics.     

UV emission properties of highly Pr3+-doped YAG epitaxial waveguides

In this work we present and discuss the dependence of ultraviolet (UV) photoluminescence of praseodymium ion (Pr³⁺):YAG crystalline waveguides, produced by liquid phase epitaxy, on activator concentration. Praseodymium level influence on UV fluorescence intensity, transition linewidth and dynamics was carefully investigated in order to better understand the nature of processes shaping both the interconfigurational d–f emission and intraconfigurational f–f emissions starting from the ³P₀ excited state. The pathways and the role of interconfiguration cross-relaxation in quenching of the UV 4f5d emission are analyzed.     

Luminescence from the Pr 4f5d and S0 states in LiLaP4O12

The photoluminescence and excitation spectra of Pr³⁺ activated LiLaP₄O₁₂ has been investigated in the 10-300 K temperature region. At all temperatures, the luminescence consists of optical transitions emanating from both the Pr³⁺ 4f¹5d¹ and the ¹S₀ states. However, at low temperatures the emission spectrum is dominated by the intraconfiguration emission transitions emanating from the Pr³⁺¹S₀ state. With increasing temperature, there is an exchange of intensity between the two emitting states; emission transitions from the ¹S₀ state exhibit strong intensity quenching while the 4f¹5d¹→4f² emission transitions reveal intensity gain. These results are explained on the basis of thermal population of the 4f¹5d¹ state by the ¹S₀ state. The energy barrier of 0.05 eV (403 cm⁻¹) for the nonradiative process is determined from the temperature dependence of the ¹S₀ lifetime.     

Effect of local environment and Sm-codoping on the luminescence properties in the Eu-doped potassium tungstate phosphor for white LEDS

The luminescence properties of Eu³⁺- and Sm³⁺-doped potassium tungstate phosphors were investigated. The K_4−3(x+y) (WO₄)₂:Eu_x³⁺,Sm_y³⁺ phosphor was produced by solid-state reactions, followed by re-firing with a flux. The phosphor showed a strong absorption in the near-UV to green region due to 4f-4f electron transitions of the Eu³⁺ and Sm³⁺ ions, generating a red emission. The excitation spectrum could be adjusted by Sm³⁺-codoping. A small amount of Sm³⁺, acting as a sensitizer, increased the energy absorption peak at 405 nm. The crystal structure and local environment around the Eu³⁺ ions were determined using the Rietveld method. The crystal structure of this phosphor was determined to be monoclinic with a space group of C2/c. The small Eu-0 distance in the crystal led to high energy-level splitting at the ⁵D₀→⁷F₂ transition of the Eu³⁺ ions, resulting in more emission peaks.     

Ultraviolet upconversion in Pr3+:Y2SiO5 crystal by Ar+ laser (488 nm) excitation

Ultraviolet upconversion fluorescence band (260–350 nm) has been observed from Pr³⁺:Y₂SiO₅ pumped by Ar⁺ ion laser (488 nm). Power dependence of the fluorescence emitted from 4f5d, ³P₀ and ¹D₂ were measured. The upconversion mechanism was analyzed using the rate equations with a simplified three level model. It appears that excited state absorption (ESA) is the dominant upconversion process for lower Pr³⁺ concentration and energy transfer upconversion (ETU) is dominant for higher Pr³⁺ concentration.     

New measurements of the emission spectra of Sm2+ in KMgF3 and NaMgF3 crystals

The fluorescence of divalent samarium in KMgF₃ and NaMgF₃ crystals is investigated. The emission is observed to originate from transitions between the ⁵D_J, and ⁷F_J multiplets of the 4?⁶ configuration. More precisely, the lowest ⁵D_J level, ⁵D₀, appears to be the most efficient emitting level in the temperature range 4–300K. Contrary to what has been reported elsewhere, the Sm²⁺ fluorescence in both crystals does not exhibit any broad band emission even at room temperature. The great number of lines in the ⁵D₀→⁷F_J patterns gives evidence of the multiple-center origin of the fluorescence.     

Green emission from Tb-doped SrSi2O2N2 phosphors under ultraviolet light irradiation

Tb-doped SrSi₂O₂N₂ phosphors with promising luminescent properties were synthesized by the conventional solid-state reaction method, characterized by powder X-ray diffraction and studied by photoluminescence excitation and emission spectra. The synthesized materials exhibited a weak blue emission and a strong green emission in the region of 400-470 nm and 480-650 nm, which are attributed to ⁵D₃→⁷F_j (j=5, 4, 3) and ⁵D₄→⁷F_j (j=6, 5, 4, 3) transitions of Tb³⁺, respectively. The green emission from ⁵D₄→⁷F₅ at 543 nm showed the highest intensity under the optimized concentration of 0.1 mol, after which the quenching concentration became relevant. The quenching behavior of the emission of Tb³⁺ was explained by the cross-relaxation of its excited state.     

Concentration-dependent luminescence of Tb ions in high calcium aluminosilicate glasses

This study deals with the results on the concentration-dependent fluorescence properties of Tb³⁺-doped calcium aluminosilicate (CAS) glasses of composition (100−x)(58SiO₂–23CaO–5Al₂O₃–4MgO–10NaF in mol%)-x Tb₂O₃ (x=0, 0.25, 0.5, 1, 2, 4, 8, 16, 24, 32, 40 in wt%). The FTIR reflectance spectra suggested the role of dopant ions as network modifiers in the glass network. The fluorescence spectra of low Tb³⁺-doped glasses have revealed prominent blue and green emissions from ⁵D₃ and ⁵D₄ excited levels to ⁷F_j ground state multiplet, respectively. The glass with 2 wt% of Tb₂O₃ has exhibited maximum intensity of blue emission from ⁵D₃ level, while green emission from ⁵D₄ level has increased linearly up to 24 wt% and showed reduction in the rate of increase for higher Tb₂O₃ concentrations. The concentration quenching of blue emission (⁵D₃→⁷F_j) is attributed mainly to the resonant energy transfer (RET) assisted cross-relaxation (CR) among the excited and nearest neighbour unexcited Tb³⁺ ions in the glass matrix. The decline in rate of increase of green emission (⁵D₄→⁷F_j) at higher concentrations has been explained due to a possible occurrence of cooperative energy transfers leading to 4f⁸→4f⁷5d transition interactions. The blue and green emission decay kinetics have been recorded to compute the excited level (⁵D₃ and ⁵D₄) lifetimes, which confirmed the Tb³⁺ concentration quenching of the blue emission in these glasses.