Energy transfer and energy level decay processes of Er3+ in water-free tellurite glass

This report details the fundamental spectroscopic properties of a new class of water-free tellurite glasses studied for future applications in mid-infrared light generation. The fundamental excited state decay processes relating to the ⁴I_11/2 → ⁴I_13/2 transition in singly Er³⁺-doped Tellurium Zinc Lanthanum glass have been investigated using time-resolved fluorescence spectroscopy. The excited state dynamics was analyzed for Er₂O₃ concentrations between 0.5 mol% and 4 mol%. Selective laser excitation of the ⁴I_11/2 energy level at 972 nm and selective laser excitation of the ⁴I_13/2 energy level at 1485 nm has established that in a similar way to other Er³⁺-doped glasses, a strong energy-transfer upconversion by way of a dipole–dipole interaction between two excited erbium ions in the ⁴I_13/2 level populates the ⁴I_11/2 upper laser level of the 3 μm transition. The ⁴I_13/2 and ⁴I_11/2 energy levels emitted luminescence with peaks located at 1532 nm and 2734 nm respectively with luminescence efficiencies of 100% and 8% for the higher (4 mol.%) concentration sample. Results from numerical simulations showed that a population inversion is reached at a threshold pumping intensity of ∼57 kW cm⁻² for a CW laser pump at 976 nm for [Er₂O₃] = 2 mol.%.     

Up-conversion luminescence of the NaYF4:Yb3+,Er3+ nanomaterials prepared with the solvothermal synthesis

Up-converting NaYF₄:Yb³⁺,Er³⁺ (x_Yb: 0.20, x_Er: 0.02) nanomaterials were prepared with a microwave assisted solvothermal synthesis to study how the synthesis parameters affect the structure and up-conversion luminescence of the materials and thus their usability as labels in biomedical applications. The purity of the materials was studied with Fourier transform infra-red (FT-IR) spectroscopy and the particle size and morphology with transmission electron microscopy (TEM). The crystal structure was characterized with X-ray powder diffraction (XPD) and the crystallite sizes were calculated with the Scherrer formula. Up-conversion luminescence and luminescence decays were studied with near infra-red (NIR) laser excitation at 970 nm.The presence of the oleic acid was observed in the FT-IR spectra. The TEM images showed small quasi-spherical nanoparticles as well as long nanorods. The XPD measurements revealed that both cubic and hexagonal forms of NaYF₄ were present in the materials. The crystallite sizes ranged from ca. 20 to over 150 nm for the cubic and hexagonal phases, respectively. The characteristic up-conversion luminescence of Er³⁺ in red (640–685 nm; ⁴F_9/2 → ⁴I_15/2) and green (515–560 nm; ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) wavelengths was observed. The most intense luminescence and the longest luminescence emission lifetime were obtained with the material annealed for 12 h at 177 °C with 1.8 MPa pressure due to the predominance of the well-crystallized hexagonal form of NaRF₄ (R: Y, Yb, Er).     

Effect of processing parameters on structural,morphological and optical Y2O3:Yb3+/Ho3+ powders characteristics

Rod-like and flake-like up-converting Y₂O₃:Yb³⁺/Ho³⁺ particles which are composed of nanoparticles with size less than 100 nm, are prepared by a simple hydrothermal processing at 473 K (3 h) followed by additional thermal treatment at 1373 K (3 and 12 h). The effect of precursor pH value on the formation of Y₂O₃:Yb³⁺/Ho³⁺ is followed through X-ray powder diffractometry (XRPD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Structural refinement confirms formation of the cubic bixbyte structure (S.G. Ia-3) with the non-uniform accommodation of dopants at C₂ and S₆ cationic sites. Under 978 nm laser excitation, strong green (530–570 nm) up-conversion is observed in all samples. The emission shows a decrease in intensity with an increase in external temperature, indicating FIR (fluorescence intensity ratio) based temperature sensing behavior of 0.52% for the ⁵F₄ → ⁵I₈/⁵S₂ → ⁵I₈ transitions.     

The luminescent properties of Er3+–Yb3+-doped fluorophosphate fiber glass preforms at high temperatures

Optical properties of fluorophosphate Er³⁺–Yb³⁺ fiber preforms with different concentrations of ErF₃ and YbF₃ are investigated in the temperature interval 25–300 °C. The temperature-dependent absorption spectra and luminescence at 1535 nm (under the λ = 970 nm excitation) spectra as well as the ⁴I_13/2 → ⁴I_15/2 luminescence decay times are used to compute the luminescence cross-section σ_e(λ). Our results show that in the range of the temperature investigated the quenching effect due to the temperature increase weakly affects the luminescence cross-section and decay time, which make these materials promising for fiber-optics applications.     

Crystal growth and spectral properties of pure and Co2+-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Enhanced emission of 2.7 μm from Er3+/Nd3+-codoped LiYF4 single crystals

An Er³⁺/Nd³⁺ co-doped LiYF₄ single crystal of ～Φ 12 mm × 95 mm size with high quality was grown by a Bridgman method. The luminescent properties of the crystals with different Er³⁺ and Nd³⁺ concentrations were studied. Compared with the Er³⁺ single-doped LiYF₄ crystal extremely enhanced emission at 2.7 μm from the Er³⁺/Nd³⁺ co-doped LiYF₄ was observed upon excitation of an 800 nm laser diode. Meanwhile, the green up-conversion emission and near infrared emission at 1.5 μm from Er³⁺ in the co-doped crystals were effectively restricted. The luminescent mechanisms for the Er³⁺/Nd³⁺ co-doped crystals were analyzed and the possible energy transfer processes were proposed. The energy transfer efficiencies for (Er³⁺:⁴I_13/2, Nd³⁺:⁴I_9/2) → (Er³⁺:⁴I_15/2, Nd³⁺:⁴I_15/2) and (Nd³⁺:⁴F_3/2, Er³⁺:⁴I_15/2) → (Nd³⁺:⁴I_9/2, Er³⁺:⁴I_9/2) were calculated. It was found that Er³⁺/Nd³⁺ co-doped single crystal may be a potential host for 2.7 μm lasers.     

Ag nanoparticles enhanced near-IR emission from Er3+ ions doped glasses

Vitreous materials containing rare-earth (RE) ions and metallic nanoparticles (NPs) attract considerable interest because the presence of the NPs may lead to an intensification of luminescence. In this work, the characteristics of 1.54 μm luminescence for the Er³⁺ ions doped bismuthate glasses containing Ag NPs were studied under 980 nm excitation. The surface plasmon resonance (SPR) band of Ag NPs appears from 500 to 1500 nm. Transmission electron microscopic (TEM) image reveals that the Ag NPs are dispersed homogeneously with the size from 2 to 7 nm. The strength parameters Ω_t(t = 2, 4, 6), spontaneous emission probability (A), radiative lifetime (τ) and stimulated emission section (σ_em) of Er³⁺ ions were calculated by the Judd–Ofelt theory. When the glass contains 0.2 wt% AgCl, the 1.54 μm fluorescence intensity of Er³⁺ reaches a maximum value, which is 7.2 times higher than that of glass without Ag NPs. The Ag NPs embedded glasses show significantly fluorescence enhancement of Er³⁺ ions by local field enhancement from SPR.     

Spectroscopic properties of HoAl3(BO3)4 single crystal

The Judd–Ofelt theory has been applied to analyze absorption spectra of Ho³⁺ ion in HoAl₃(BO₃)₄ measured in spectral range 300–700 nm at room temperature. The Judd–Ofelt spectroscopic parameters have been determined as: Ω₂ = 18.87 × 10⁻²⁰ cm², Ω₄ = 17.04 × 10⁻²⁰ cm², Ω₆ = 9.21 × 10⁻²⁰ cm². These parameters have been used to calculate radiative lifetimes and branching ratios of the luminescence manifolds. Three luminescent bands were found in the spectral range 450–700 nm ascribed to transitions from the ⁵F₅, (⁵F₄, ⁵S₂) and ³K₈ states to the ground state ⁵I₈. Experimental intensities of these luminescence transitions were compared with those calculated by using Judd–Ofelt theory and the system of kinetic equations for populations of starting luminescing states. Probabilities of radiativeless transitions were evaluated from this comparison.     

Gold nanoparticles assisted structural and spectroscopic modification in Er3+-doped zinc sodium tellurite glass

Achieving enhanced spectroscopic properties of rare earth doped inorganic glasses by embedding metallic nanoparticles of controlled sizes is a challenging task. We report the gold (Au) NPs assisted modifications in structural and spectroscopic properties of melt-quench synthesized Er³⁺ doped zinc sodium tellurite glass. The growth of NPs is stimulated via time varying heat treatment at 300 °C. XRD patterns confirm the amorphous nature of glasses and TEM images manifest the growth of gold NPs with sizes between 6.1 and 10.7 nm. The heat treatment time dependent variations in physical properties are ascribed to the alteration in bonding of non-bridging oxygen ions. The UV–VIS–NIR spectra reveal six absorption peaks centered at 488, 523, 655, 800, 973 and 1533 nm corresponding to the transition from ground state of ⁴I_15/2 to ⁴F_7/2, ²H_11/2, ⁴F_9/2, ⁴I_9/2, ⁴I_11/2, and ⁴I_13/2 excited states of Er³⁺ ions, respectively. Surface plasmon resonance (SPR) bands are observed in the range of 618–632 nm. Judd–Ofelt analyses demonstrate a significant increase of spectroscopic quality factors (0.86–1.05) and branching ratio (0.62–92.38%). The up-conversion emission spectra of Er³⁺ exhibit three prominent peaks of reasonable green (502 nm), a moderate green (546 nm) and a strong red (629 nm). An enhancement in the red band luminescence intensity by a factor of 8.19 and 8.54 times are achieved for 2 and 4 h of heat treatments, respectively. This enhancement is attributed to the SPR effects of gold NPs producing an intense local field in the proximity of Er³⁺ ions and subsequent energy transfer between RE ions and NPs. The FTIR spectra display the presence of vibrational modes for ZnO₄ bonds, Te–O bond in TeO₃ (tp) and TeO₄ (tbp) units and the hydroxyl groups. Excellent features of the results suggest that our method constitute a basis for tunable growth of gold NPs which is exceedingly useful for the optimization of optical and structural properties.     

Growth and spectroscopic properties of Er-doped Li3Ba2Y3(MoO4)8 crystal

Er³⁺:Li₃Ba₂Y₃(MoO₄)₈ crystal has been grown by the top seeded solution growth method (TSSG) from a flux of Li₂MoO₄ and its morphology was analyzed. The polarized absorption spectra, fluorescence spectra and fluorescence decay curves of the crystal were measured. Based on the Judd-Ofelt (J-O) theory, spectroscopic parameters of Er³⁺:Li₃Ba₂Y₃(MoO₄)₈ crystal, including the oscillator intensity parameters Ω_t (t = 2, 4, 6), spontaneous emission probabilities, fluorescence branching ratios, and radiative lifetimes were calculated and analyzed. Stimulated emission cross-sections of the ⁴I_13/2 → ⁴I_15/2 transition were estimated by the reciprocity method (RM) and the Fuchtbauer-Ladenburg (F-L) formula. Five up-conversion fluorescence bands around 490, 530, 550, 660 and 800 nm were observed with 977 nm excitation, and the possible up-conversion mechanisms were proposed.     

Spectroscopic analysis of a novel Nd3+-activated barium borate glass for broadband laser amplification

Spectroscopic parameters of a novel Nd³⁺-activated barium borate (BBONd) glass have been analyzed for broadband laser amplification. The Judd–Ofelt (JO) intensity parameters were determined through a systematic analysis of the absorption spectrum of Nd³⁺ ions in the BBONd glass. High values of the JO intensity parameters reveal a great centro-symmetrical loss of the Nd³⁺ sites and high covalency degree of the ligand field. The very high Ω₆ intensity parameter value makes evident both a great structural distortion of the Nd³⁺ sites and a strong electron–phonon coupling between Nd³⁺ and free OH⁻ ions, which is consistent with the phonon energy maximum (3442.1 cm⁻¹) recorded by Raman spectroscopy. This strong electron–phonon coupling favors high effective bandwidth and gain bandwidth values of the laser emission (⁴F_3/2 → ⁴I_11/2) of Nd³⁺ ions. The electric-dipole oscillator strengths of all the Nd³⁺ absorption transitions, and in particular that of the hypersensitive transition (⁴I_9/2 → ⁴G_5/2), are enhanced by this great structural distortion of the host. Broadband laser amplification of the ⁴F_3/2 → ⁴I_11/2 emission (1062 nm) of Nd³⁺ ions in the BBONd glass pumped at 805 nm (⁴I_9/2 → ⁴F_5/2 + ²H_9/2) is evaluated through the main fluorescent parameters in competition with non-radiative processes. In general, the BBONd glass exhibits spectroscopic parameters comparable with those reported in the literature for broadband laser amplification into the IR region.     

Up-conversion luminescence properties of Y2O2S:Yb3+,Er3+ nanophosphors

Up-converting yttrium oxysulfide nanomaterials doped with ytterbium and erbium (Y₂O₂S:Yb³⁺,Er³⁺) were prepared with the flux method. The precursor oxide materials were prepared using the combustion synthesis. The morphology of the oxysulfides was characterized with transmission electron microscopy (TEM). The particle size distribution was 10–110 nm, depending on the heating temperature. According to the X-ray powder diffraction (XPD), the crystal structure was found hexagonal and the particle sizes estimated with the Scherrer equation agreeded with the TEM images. Upon the 970 nm infrared (IR) laser excitation, the materials yield moderate green ((²H_11/2, ⁴S_3/2) → ⁴I_15/2 transition) and strong red (⁴F_9/2 → ⁴I_15/2) luminescence. The green luminescence was enhanced with respect to the red one by an increase in both the crystallite size and erbium concentration due to the cross-relaxation (CR) processes. The most intense up-conversion luminescence was achieved with x_Yb and x_Er equal to 0.10 and 0.005, respectively. Above these concentrations, concentration quenching occurred.     

Photoluminescence,photo-stimulated luminescence and thermoluminescence properties of CaB2O4 crystals activated with Ce3+

Photoluminescence (PL), photo-stimulated luminescence (PSL), and thermoluminescence (TL) properties of a Ce-doped CaB₂O₄ crystal were studied. The Ce-doped crystal was prepared by the simple solidification method using a Pt crucible under nitrogen atmosphere. A PL emission band in the 350–370 nm wavelength range was obtained under excitation at 325 nm owing to the 5d (t_2g)–4f (²F_5/2, ²F_7/2)-allowed transition of the Ce³⁺ emission center. The fluorescence quantum efficiency and the decay time of Ce³⁺ were estimated to be about 70% and 29 ns, respectively. The 5d–4f emission band of Ce³⁺ also appeared in the 350–370 nm wavelength range in the TL and PSL spectra. Good linear TL and PSL responses were observed in the 1–1000 mGy and 1–10,000 mGy X-ray dose range, respectively.     

Optical studies on X and γ irradiated vacuum grown CsBrI:Eu2+ crystals

CsBr_0.9I_0.1:Eu²⁺ crystals were grown by Bridgman technique. Optical absorption spectrum of the unirradiated CsBr_0.9I_0.1:Eu²⁺ crystals show absorption bands at 270 nm and 340 nm. Irradiated CsBr_0.9I_0.1:Eu²⁺ shows single F band for F(Br⁻) and F(I⁻) centers at 730 nm. Conversion of Eu²⁺ to Eu³⁺ after irradiation is confirmed by optical absorption technique. Sharp and single Photoluminescence (PL) emission band is observed at 440 nm for CsBr_0.9I_0.1:Eu²⁺ crystals. Photostimulated Luminescence (PSL) emission band observed for CsBr_0.9I_0.1:Eu²⁺ crystals at 442 nm due to excitation at 730 nm shows that the F centers are photostimulable. PSL emission intensity increases linearly with irradiation dose up to 2.5 Krad.     

Spectroscopic properties of Sm3+-doped oxy-fluoride powders with various Sm3+ concentration and sintering temperature

Sm³⁺-doped oxy-fluoride (OFSm) powders are prepared by the melt quenching technique and characterized using FE-SEM, optical absorption and emission techniques. Spectroscopic properties of Sm³⁺-doped oxy-fluoride powders with different Sm³⁺ concentration and sintering temperature are presented and discussed by using the absorption, emission measurements. The Judd–Ofelt intensity (J–O) parameters (Ω_λ, where λ = 2, 4 and 6), measured from the experimental oscillator strengths of the absorption spectra, are used to evaluate the radiative parameters of the fluorescence transitions. Intense orange emission can be obtained when excited with 325 nm wavelength by increasing the sintering temperature to 1400 °C. Ratio of fluorescence intensities arising from the two closing lying ⁴F_3/2 and ⁴G_5/2 levels is studied, concentration quenching has been noticed beyond 2 mol% of Sm³⁺ ions concentration. The excellent spectroscopic properties along with the outstanding thermal stability suggest that the OFSm03 powders may become an attractive laser material to exhibit efficient visible lasing emission in the orange spectral region.     

Frequency upconversion properties of Er3+/Yb3+-codoped lead–germanium–bismuth oxide glasses

The frequency upconversion properties of Er³⁺/Yb³⁺-codoped heavy metal oxide lead–germanium–bismuth oxide glasses under 975 nm excitation are investigated. Intense green and red emission bands centered at 536, 556 and 672 nm, corresponding to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively, were simultaneously observed at room temperature. The influences of PbO on upconversion intensity for the green (536 and 556 nm) and red (672 nm) emissions were compared and discussed. The optimized rare earth doping ratio of Er³⁺ and Yb³⁺ is 1:5 for these glasses, which results in the stronger upconversion fluorescence intensities. The dependence of intensities of upconversion emission on excitation power and possible upconversion mechanisms were evaluated and analyzed. The structure of glass has been investigated by means of infrared (IR) spectral analysis. The results indicate that the Er³⁺/Yb³⁺-codoped heavy metal oxide lead–germanium–bismuth oxide glasses may be a potential materials for developing upconversion fiber optic devices.     

Synthesis and two-color emission properties of BaGd2(MoO4)4:Eu3+,Er3+,Yb3+ phosphors

Eu³⁺, Er³⁺ and Yb³⁺ co-doped BaGd₂(MoO₄)₄ two-color emission phosphor was synthesized by the high temperature solid-state method. The structure of the sample was characterized by XRD, and its luminescence properties were investigated in detail. Under the excitation of 395 nm ultraviolet light, the BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ phosphor emitted an intense red light at 595 and 614 nm, which can be attributed to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺, respectively. The phosphor will also show bright green light under 980 nm infrared light excitation. The green emission peaks centred at 529 and 552 nm, were attributed to ⁴H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺, respectively. It indicated that the two-color emission can be achieved from the same BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ host system based on the different pumping source, 395 nm UV light and 980 nm infrared light, respectively. The obtained results showed that this kind of phosphor may be potential in the field of multi-color fluorescence imaging and anti-counterfeiting.     

Compositional variation of photoluminescence from Mn doped MgAl2O4 spinel

Spinel (MgAl₂O₄) crystals doped with 1.0% Mn have been grown by floating zone (FZ) technique with various Mg compositions, x = MgO/Al₂O₃, from 0.2 to 1.0. Compositional variations of photoluminescence are evaluated for a fluorescence thermometer application using crystals grown. Strong photoluminescence (PL) peak is observed at λ from 512 to 520 nm from the crystals grown from compositions, x, from 0.3 to 1.0. Peak wavelength of PL increases linearly from 512 to 520 nm with x. Weak PL peaking at λ = 750 nm is also observed from the specimens. Compositional variations of PL are considered to be due to the variation of crystal field surrounding the Mn²⁺ ions. The variation of crystal field strength agrees with the compositional variation of lattice constant.     

Spectroscopic properties and energy transfer in Er–Tm co-doped bismuth silicate glass

In this paper, we investigate the spectroscopic properties of and energy transfer processes in Er–Tm co-doped bismuth silicate glass. The Judd–Ofelt parameters of Er³⁺ and Tm³⁺ are calculated, and the similar values indicate that the local environments of these two kinds of rare earth ions are almost the same. When the samples are pumped at 980 nm, the emission intensity ratio of Tm:³F₄ → ³H₆ to Er:⁴I_13/2 → ⁴I_15/2 increases with increased Er³⁺ and Tm³⁺ contents, indicating energy transfer from Er:⁴I_13/2 to Tm:³F₄. When the samples are pumped at 800 nm, the emission intensity ratio of Er:⁴I_13/2 → ⁴I_15/2 to Tm:³H₄ → ³F₄ increases with increased Tm₂O₃ concentration, indicating energy transfer from Tm:³H₄ to Er:⁴I_13/2. The rate equations are given to explain the variations. The microscopic and macroscopic energy transfer parameters are calculated, and the values of energy transfer from Er:⁴I_13/2 to Tm:³F₄ are found to be higher than those of the other processes. For the Tm singly-doped glass pumped at 800 nm and Er–Tm co-doped glass pumped at 980 nm, the pumping rate needed to realize population reversion is calculated. The result shows that when the Er₂O₃ doping level is high, pumping the co-doped glass by a 980 nm laser is an effective way of obtaining a low-threshold ∼2 μm gain.     

Optical properties of Nd3+ and Er3+ ions in TeO2–WO3–PbO–La2O3 glasses

Multicomponent telluride-tungstate glasses containing Nd³⁺ and Er³⁺ ions were studied experimentally at 77 and 293 K using spectroscopic methods. The Judd–Ofelt intensity parameters were derived from the absorption spectra and used to calculate the radiative lifetimes and branching ratios. The quantum efficiency η = 0.95 of the ⁴F_3/2 level of Nd³⁺ ion is higher than the typical value of other tellurite-based glasses. For low concentration of Er³⁺ ions, the luminescence decay of the ⁴S_3/2 and ⁴I_11/2 levels is governed by radiative transitions and multiphonon relaxation involving the Te-O highest energy vibrations.