Resonant energy transfer and cross relaxation between Sm3+ ions in LiYF4 crystals

Luminescence decay curves of Sm³⁺ ions in LiYF₄ crystals doped with 1, 5 and 10 mol% Sm³⁺ are multi-exponential, whereas that in a LiYF₄ crystal doped with 0.1 mol% Sm³⁺ is well approximated by a single exponential function with a decay time of 4.8 ms. The average luminescence decay times decrease from 4.8 to 0.60 ms with the increasing Sm³⁺ concentrations between 1 and 10 mol%. The decay curves for all crystals are found to be almost independent of the temperature between 15 and 300 K. The decrease of the decay times for the higher Sm³⁺ concentrations indicates energy transfer between two Sm³⁺ ions. Taking the crystal structure of LiYF₄ into account, it is deduced that a single-step energy transfer process for the 1 and 5 mol% Sm³⁺ concentrations occurs from a Sm³⁺ ion at the origin of (0 0 0) to one of the Sm³⁺ ions substituting for the first nearest neighbor Y³⁺ sites and beyond within a sphere with an approximate radius of less than 0.7 nm. On the other hand, a multi-step energy transfer process dominates for the highest concentration (10 mol%) because the calculated average distance between two Sm³⁺ ions in the 10 mol% Sm³⁺ sample is comparable with the migration length of the single-step energy transfer process estimated from the 1 and 5 mol% Sm³⁺ samples.     

Dopant occupancy and optical properties of Er3+ in Er/Zn-codoped lithium niobate crystal

The effect of Zn²⁺ ion on the dopant occupancy and optical characteristic of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal is reported. The intense 1.54 μm and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO₃ crystal. The OH^? absorption and the time-resolved spectra show that the Zn²⁺ codoping decreases the threshold concentration of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal. The experimental results here imply that the potential application of Er³⁺-doped LiNbO₃ crystal can be designed and optimized on the basis of the theoretical investigations.     

Preparation and photocatalytic degradation of erbium doped titanium dioxide nanorods

Photocatalytic degradation of methylene blue (MB) in water was examined using Er³⁺-doped TiO₂ (Er–TiO₂) nanorods prepared by a sol–gel derived electrospinning, calcination, and subsequent mechanical grinding. Different concentrations of Er dopant in the range of 0–1.0 mol% were synthesized to evaluate the effect of Er content on the photocatalytic activity of TiO₂. Among Er³⁺–TiO₂ catalysts, the 0.7 mol% Er³⁺–TiO₂ catalyst showed the highest MB degradation rate. The degradation kinetic constant (k) increased from 1.0 × 10^?3 min^?1 to 5.1 × 10^?3 min^?1 with the increase of Er³⁺ doping from 0 to 0.7 mol%, but decreased down to 2.1 × 10^?3 min^?1 when Er³⁺ content was 1.0 mol%. It can be concluded that the degradation of MB under UV radiation was more efficient with Er³⁺–TiO₂ catalyst than with pure TiO₂. The higher activity might be attributed to the transition of 4f electrons of Er³⁺ and red shifts of the optical absorption edge of TiO₂ by erbium ion doping.     

Optical properties of Er3+-doped strontium barium niobate nanocrystals obtained by thermal treatment in glass

Measurements of the optical properties of Er³⁺ ions in strontium barium niobate glass and glass ceramics have been carried out. The glasses have been fabricated using a melt-quenching method, and the glass ceramic samples have been obtained from the glass precursor by a thermal treatment. The ceramic samples formed by a glassy phase, and a crystalline phase contains nanocrystals of Sr_1?xBa_xNb₂O₆ (SBN) doped with Er³⁺ ions with a mean size of ～50 nm, as confirmed with XRD. Green up-conversion emission has been obtained under excitation at 800 nm, and the temporal evolution of this emission has been reported with the purpose of determining the involved up-conversion mechanism. These optical measures have confirmed that the Er³⁺ ions have been incorporated into the SBN matrix, after a thermal treatment, which produced an increment of the up-conversion efficiency.     

Improved photoluminescence of BaMgAl10O17 blue phosphor prepared by spray pyrolysis

BaMgAl₁₀O₁₇:Eu²⁺ (BAM) blue phosphor particles with improved photoluminescence (PL) intensity under vacuum ultraviolet (VUV) excitation were prepared by a spray pyrolysis process. In order to improve the PL intensity, Er³⁺ and Nd³⁺ ions were used as co-doping elements. The VUV characteristics of BAM:Eu²⁺, M⁺ (M=Er, Nd) were monitored with varying the Er³⁺ and Nd³⁺ content in order to find the optimal co-doping concentration when they were prepared by spray pyrolysis. It was found that doping Er³⁺ or Nd³⁺ enhances the PL intensity of BAM:Eu²⁺ blue phosphor particles. In particular, the M³⁺ doping effect on the PL intensity was pronounced when the prepared BAM:Eu²⁺, M³⁺ particles were excited by 172 nm VUV. The maximum intensity was obtained when the M³⁺ content was 1.0 at% with respect to Ba element. The PL intensity of BAM:Eu²⁺, M⁺ (M=Er³⁺, Nd³⁺) particles was also further improved by producing them in a spherical shape, which was successfully achieved by controlling the spray solution. The optimized BAM:Eu²⁺, M⁺ particles had about 10% higher PL intensity than that of the commercial particles, which are made by a conventional solid-state reaction.     

Novel EGCG assisted ultrasound synthesis of self-assembled Ca2SiO4:Eu3+ hierarchical superstructures: Photometric characteristics and LED applications

This paper reports for the first time ultrasound, EGCG assisted synthesis of pure and Eu³⁺ (1–5 mol%) activated Ca₂SiO₄ nanophosphors having self-assembled superstructures with high purity. The shape, size and morphology of the product were tuned by controlling influential parameters. It was found that morphology was highly dependent on EGCG concentration, sonication time, pH and sonication power. The probable formation mechanism for various hierarchical superstructures was proposed. The PL studies of Ca₂SiO₄:Eu³⁺ phosphors can be effectively excited by the near ultraviolet (UV) (396 nm) light and exhibited strong red emission around 613 nm, which was attributed to the Eu³⁺ (⁵D₀ → ⁷F₂) transition. The concentration quenching phenomenon was explained based on energy transfer between defect and Eu³⁺ ions, electron–phonon coupling and Eu³⁺–Eu³⁺ interaction. The Judd–Ofelt intensity parameters and radiative properties were estimated by using PL emission spectra. The photometric studies indicate that the obtained phosphors could be a promising red component for possible applications in the field of white light emitting diodes.     

Color tunable emission from (GdxY1−x)2O3: Er3+, Yb3+ phosphor prepared by combustion method

The (Gd_xY_1?x)₂O₃: Er³⁺, Yb³⁺ [x=0.0, 0.1, 0.5, 0.9, 1.0] phosphor samples with 0.5 mol% concentration of Er³⁺ and 3.0 mol% of Yb³⁺, have been prepared using combustion route. The effect of variation of composition on the morphology, crystallinity and photoluminescence characteristics of the material has been investigated. The samples were post-heated at a temperature 1200 °C, for 5 h. We find systematic color tunability from red to green with an increase of Gd₂O₃ content in Y₂O₃ lattice. Further, the post-heated samples show an enhancement of fluorescence intensity for more than fifteen times. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence measurement and Fourier transform infrared (FTIR) techniques in order to find out the structural changes in host lattice. An increase in crystallite size has been marked with increasing Gd content while FTIR analysis explains the reason of variation in the fluorescence of rare earth ions in different host matrices.     

Upconversion photoluminescence properties of SrY2(MoO4)4:Er3+/Yb3+ phosphors synthesized by a cyclic microwave-modified sol–gel method

SrY_2−x(MoO₄)₄:Er³⁺/Yb³ phosphors with doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0.05, 0.1, 0.2 and Yb³⁺ = 0.2, 0.45) have been successfully synthesized by a cyclic microwave-modified sol–gel method, and the upconversion photoluminescence properties have been investigated. Well-crystallized particles showed a fine and homogeneous morphology with particle sizes of 1–3 μm. Under excitation at 980 nm, SrY₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited a strong 525-nm, weak 550-nm emission bands in the green region, and a very weak 655-nm emission band in the red region. The possible mechanism of the green and red emissions was discussed in detail under consideration of a two-photon process. The Raman spectra of the particles indicated the presence of strong peaks at both higher and lower frequencies.     

Thermo,Iono and photoluminescence properties of 100 MeV Si7+ ions bombarded CaSiO3:Eu3+ nanophosphor

This paper reports on the thermo (TL), iono (IL) and photoluminescence (PL) properties of nanocrystalline CaSiO₃:Eu³⁺ (1–5 mol %) bombarded with 100 MeV Si⁷⁺ ions for the first time. The effect of different dopant concentrations and influence of ion fluence has been discussed. The characteristic emission peaks ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions was recorded in both PL (1×10¹¹–1×10¹³ ions cm^?2) and IL (4.16×10¹²–6.77×10¹² ions cm^?2) spectra. It is observed that PL intensity increases with ion fluence, whereas in IL the peaks intensity increases up to fluence 5.20×10¹² ions cm^?2, then it decreases. A well resolved TL glow peak at ～304 °C was recorded in all the ion bombarded samples at a warming rate of 5 °C s^?1. The TL intensity is found to be maximum at 5 mol% Eu³⁺ concentration. Further, TL intensity increases sub linearly with shifting of glow peak towards lower temperature with ion fluence.     

Spectroscopic properties of Sm3+ ions in lead fluorophosphate glasses

The Sm³⁺-doped lead fluorophosphate glasses of composition 44P₂O₅–17K₂O–9Al₂O₃–(24?x)PbF₂–6Na₂O–xSm₂O₃, where x=0.01, 0.05, 0.1, 0.5, 1.0 and 2.0 mol%, have been prepared by conventional melt quenching technique and are characterized through differential thermal analysis, Raman, absorption and emission spectra and decay rate measurements. Free-ion Hamiltonian model for energy level analysis and Judd–Ofelt theory for spectral intensities have been used to analyze the spectroscopic properties of Sm³⁺ ions in lead fluorophosphate glasses. The decay rates for the ⁴G_5/2 level of Sm³⁺ ions have been measured and are found to be single exponential at lower concentration (≤0.1 mol% Sm₂O₃) and turn into non-exponential at higher concentrations (≥0.5 mol% Sm₂O₃) due to energy transfer through cross-relaxation. The experimental lifetimes for ⁴G_5/2 level of Sm³⁺ ions are found to decrease from 2.54 to 0.92 ms when the concentration increased from 0.01 to 2.0 mol% Sm₂O₃ due to energy transfer. In order to know the nature of the energy transfer mechanism, the non-exponential decay rates are well fitted to Inokuti–Hirayama model for S=6, which indicates that the energy transfer process is of dipole–dipole type.     

The influence of Eu3+ doping on photoluminescent properties of red emitting phosphor YInGe2O7:Eu3+ by microwave assisted and conventional sintering method

This paper describes an investigation of the crystalline morphology and photoluminescent properties of YInGe₂O₇ powders doped with different Eu³⁺ concentrations using microwave assisted sintering and conventional sintering. X-ray powder diffraction analysis confirmed the formation of monoclinic YInGe₂O₇ structure as YInGe₂O₇:Eu³⁺ powders were sintered at 1200 °C in microwave furnace for 1 h, and the raw material phase of Y₂O₃ was observed when Eu³⁺ concentration was below 30 mol%. Scanning electron microscopy showed microwave assisted sintering results in smaller particle size and more uniform grain size distribution. In the photoluminescent (PL) studies, the concentration quenching effect was observed under the excitation at 393 nm, but not under the excitation at CTS band. The ⁵D₀→⁷F₂ transition (620 nm), exhibits a non-exponential decay behavior as YInGe₂O₇:Eu³⁺ powders were sintered by microwave with the Eu³⁺ concentration higher than 50 mol%.     

Positive influence of Tm3+ on effective Er3+: 3 μm emission in fluoride glass under 980 nm excitation

Er³⁺ and Tm³⁺ singly doped and codoped new fluoride glasses were prepared by traditional melt-quenching method. Efficient 3 μm emission was obtained under 980 nm laser excitation. It is worthy to notice that one of the two ions can be the sensitizer to the other one by depressing the Er³⁺: 1.5 μm emission through the energy transfer process from Er³⁺:⁴I_13/2 level to Tm³⁺:³F₄ level. On the basis of measured absorption spectra, the Judd-Ofelt intensity parameters and radiation emission probability were calculated to evaluate the spectroscopic properties. Additionally, the micro-parameters together with the phonon assistance of Er³⁺:⁴I_13/2 → Tm³⁺:³F₄ and Er³⁺:⁴I_11/2 → Tm³⁺:³H₅ processes were quantitatively analyzed by using Dexter model. The theoretical micro-parameters results meet well with the experiments which indicates that Er³⁺/Tm³⁺ codoped fluoride glass is a potential kind laser glass for 3 μm laser.     

Luminescence and energy transfer in La2O3–Nb2O5–B2O3:M3+ (M=Bi,Eu, Dy) glasses

The luminescence and energy transfer processes in La₂O₃–Nb₂O₅–B₂O₃:M³⁺ (M=Bi, Eu, Dy) glasses were investigated using luminescence spectroscopy (excitation and emission, down to 4.2 K) and decay time measurements at room temperature. The observation of niobate luminescence implies a considerable degree of short- and intermediate-range order in these glasses. Energy transfer from the niobate groups to the lanthanide ions was observed for Eu³⁺, but not for Dy³⁺, suggesting that the energy transfer process occurs to the charge-transfer state of the Eu³⁺ ion, rather than to its f-levels. Inter-Eu³⁺ energy transfer was negligible in the concentration range investigated (up to 3 mol%). In contrast, cross-relaxation processes between Dy³⁺ ions were active at concentrations as low as 0.5 mol%. In the Bi³⁺ doped glasses the energy transfer was observed from the Bi³⁺ excited levels to the oxygen deficient niobate groups.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

Microwave sol–gel derived NaCaGd(MoO4)3:Er3+/Yb3+ phosphors and their upconversion photoluminescence properties

Ternary molybdate NaCaGd_1−x(MoO₄)₃:Er³⁺/Yb³⁺ phosphors with the proper doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0, 0.05, 0.1, 0.2 and Yb³⁺ = 0, 0.2, 0.45) were successfully synthesized by microwave sol–gel method for the first time. Well-crystallized particles formed after heat-treatment at 900 °C for 16 h showed a fine and homogeneous morphology with particle sizes of 3–5 μm. The optical properties were examined comparatively using photoluminescence emission and Raman spectroscopy. Under excitation at 980 nm, the doped particles exhibited a strong 525-nm emission band, a weak 550-nm emission band in the green region, which correspond to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and a very weak 655-nm emission band in the red region, which corresponds to the ⁴F_9/2 → ⁴I_15/2 transition. The optimal Yb³⁺:Er³⁺ ratio was obtained to be 9:1, as indicated by the composition-dependent quenching effect of Er³⁺ ions. The pump power dependence of upconversion emission intensity and Commission Internationale de L’Eclairage chromaticity coordinates of the phosphors were evaluated in detail.     

The influence of Zn2+ ion on the 1.5 μm laser properties of LiNbO3 crystal heavily doped with Er3+ ion

The spectral characteristics of 1.54 μm emission in a series of Zn/Er:LiNbO₃ crystals with heavy Er content and variable Zn content were reported. The inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the concentration of Er³⁺ ion in the crystal. The absorption and emission spectra of Zn/Er:LiNbO₃ crystals were measured. Based on Judd–Ofelt theory, the spectral parameters such as intensity parameters Ω_t (t=2, 4 and 6), transition strengths, radiative transition probabilities, radiative lifetime and fluorescence branching ratio have been obtained in Zn/Er:LiNbO₃ system. The emission cross section corresponding to ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ion was obtained according to Füchtbauer–Ladenburg theory. The gain cross section of Er:LiNbO₃ crystal codoped with 6 mol% Zn²⁺ ions were also discussed in this work.     

Temperature measurements inside an Er3+–Yb3+ co-doped fluoride crystal heated by a NIR laser diode and probed by red-to-green upconversion

The temperature of a transparent Cd_0.7Sr_0.3F₂: Er³⁺(4%)–Yb³⁺(6%) crystalline plate 0.3 mm thick heated by a near-infrared (974 nm) laser diode and probed by a red (652 nm) laser was accurately evaluated as a function of the infrared power absorbed by the Yb³⁺ ions.The green emission generated by the Er³⁺ ions directly excited by the red laser consists of three major lines (coming from three individual Stark levels in thermal equilibrium) whose intensities were measured according to the absorbed infrared power and the distance between the heated and probed volumes, to evaluate the heating induced by the excitation of Yb³⁺ and Er³⁺ ions at 974 nm by applying the Boltzmann's equation linking the populations of emitting levels to the temperature. In the case where the Yb³⁺ ions excited by the laser diode are situated at a distance of about 0.5 mm from the edge of the crystal and for an absorbed infrared power of 100 mw, the crystal's edge temperature is reaching 80 °C after 20 s of continuous excitation at 974 nm.     

Thermal stability and spectroscopic properties of erbium-doped niobic-tungsten–tellurite glasses for laser and amplifier devices

Er³⁺ doped niobic-tungsten–tellurite glasses doped with concentration of Er³⁺ ion up to 3 wt% were fabricated. The effect of Er³⁺ doping concentration on thermal stability and optical properties was investigated in order to obtain the most suitable rare earth content for developing 1.5 μm compact fiber amplifier pumped with a commercial telecom 980 nm laser diode. The maximum doping concentration allowed was found to be around 1.77×10²⁰ ions/cm³, for which a broad 1.5 μm emission spectra of 65 nm FWHM and a lifetime of 3.4 ms for the ⁴I_13/2 level was measured.     

Quasi-one dimensional Er3+–Yb3+ codoped single-crystal MoO3 ribbons: Synthesis,characterization and up-conversion luminescence

The quasi-one dimensional (Q1D) Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons with width range from 1 to 5 μm, and maximum length about 30 μm have been synthesized by the vapor transport method. The samples were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscope, and luminescence spectra. By a 975 nm laser diode (LD) as excitation source, the blue, green and red emission bands centered at about 408, 532, 553 and 657 nm were detected, which attributed to the ²H_9/2 → ⁴I_15/2, ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. The three-, and two-photon process was responsible for the blue, green and red up-conversion emissions mechanism for the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons, respectively. The results suggested that the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons will have potential applications in remote bio-imaging and surface enhanced Raman scattering.     

Investigation of the effect of annealing on the magnetic properties of Sn1−xEuxTe single crystals

A study of the effect of annealing on the magnetic properties of single crystals Sn_1−xEu_xTe is reported. The width of the electron paramagnetic resonance line of the crystal is found to decrease upon annealing but its g-value of 1.991 is nearly unaffected. Magnetization results indicate that the pair exchange interaction is weakly antiferromagnetic with a value of −0.67 K for the non-annealed sample and −0.29 K after annealed sample. Susceptibility measurements performed as a function of temperature also indicate the presence of EuTe clusters in the as-grown Sn_1−xEu_xTe crystals. Therefore it was deduced that the Eu²⁺ ions tend to form clusters, particularly pairs, in the as-grown crystal and these clusters disappear after annealing, as the Eu²⁺ ions occupy isolated sites in the SnTe host lattice.