Enhanced and Long‐Lived Near‐Infrared Luminescence of Er3+ Ions in Lead Borate Glass‐Ceramics Containing PbWO4 Nanocrystals

Lead tungstate PbWO₄ nanocrystals in transparent lead borate glass‐ceramics containing Er³⁺ ions were fabricated. Luminescence spectra at about 1530 nm due to main ⁴I_13/2–⁴I_15/2 laser transition of Er³⁺ ions were examined for glass samples before and after heat treatment. Near‐infrared luminescence of Er³⁺ ions in glass‐ceramics is enhanced and long‐lived in comparison to precursor glasses. It suggests that the Er³⁺ ions are partially incorporated into PbWO₄ crystalline phase.     

Evolution of Strong Red Upconversion Luminescence in Er3+‐Containing Oxy‐Fluoride Glass and Glass‐Ceramics

The Er³⁺ concentration dependencies of upconversion luminescence in oxy‐fluoride glass and glass‐ceramics containing PbF₂ nanocrystals were investigated. Strong red emission from the ⁴F_9/2 → ⁴I_15/2 transition was observed with the addition of ~0.8 mol% Er³⁺ ions, whereas ~10 mol% of Er³⁺ is required to achieve such emission in several other crystalline hosts. Intensities of red emission further increased with the formation of nanocrystals through heat treatment. The Er³⁺ ions enriched in glass and segregated preferentially inside the PbF₂ nanocrystals that decreased the distance among Er³⁺ ions and thereby facilitated energy transfer.     

Intense 2.7 µm emission of Er3+/Pr3+ doped Ga5Ge20Sb10S65 chalcogenide glass

There are numerous vital usages for mid-infrared (MIR) lasers in satellite communication, biomedicine, military, remote sensing, and environmental monitoring. In this work, a progression of Er³⁺ ions doped, Er³⁺/Pr³⁺ ions co-doped Ga₅Ge₂₀Sb₁₀S₆₅ glasses were prepared, and their physical performances and structural characteristics were examined. To understand the non-phonon-assisted energy transfer mechanism, we recorded the up-conversion and infrared fluorescence emission spectra by pumping with a commercial 980 nm LD. Then the 2.7 µm strong fluorescence signal intensity can be obtained when the doped concentration of Pr³⁺ is proper. After the doping of Pr³⁺, fluorescence lifetime results revealed that the lifetimes of the Er³⁺:⁴I_13/2 level fell dramatically from 7.33 to 1.90 ms, which experienced a much more significant decrease in lifetimes than the Er³⁺:⁴I_11/2 level. The MIR fluorescence performances were assessed by the determined J–O parameters and relative emission cross sections. Additionally, the generally huge emission cross sections and the small pump energy show that it is possible to obtain population inversion with relatively small pump energy; thus the Er³⁺/Pr³⁺ glasses have great potential to be 2.7 µm laser materials.     

Photoluminescence of Ag Nanoparticles and Tm3+ Ions in the Bismuth Germanate Glasses for the Blue Light‐Excited W‐LED

Materials containing rare‐earth ions and Ag nanoparticles (NPs) have been widely applied due to prior demonstration of increase in their luminescence properties. Here, Tm³⁺ ions‐doped bismuth germanate glasses were synthesized by a chemical reduction method based on the conventional melting‐quenching technique. The Ag NPs were facilely precipitated in the glass matrix by the chemical reduction method during the annealing process. TEM image shows that the Ag NPs are closely dispersed in the glass matrix. The luminescence properties and energy‐transfer mechanism were systematically investigated by means of absorption, emission, and excitation spectra. Significant enhancements of Tm³⁺ ions emission and a broad emission band centered at 568 nm caused by Ag NPs are observed upon 474‐nm excitation. Our research may illustrate the interactions between Tm³⁺ ions and Ag NPs and provide a simplified way to synthesize the high‐efficiency luminescent materials for the blue light‐excited W‐LEDs.     

Enhanced Up‐Conversion Luminescence in Er3+‐Doped 25GeS2·35Ga2S3·40CsCl Chalcogenide Glass–Ceramics

Enhanced luminescence in rare‐earth‐doped chalcogenide glass–ceramics is of great interest for the potential integrated optoelectronic devices. However, fundamental mechanism on the enhancement of luminescence upon crystallization remains largely unknown. We report the fabrication and characterization of wide transmission chalcogenide glass and glass–ceramics based on the 25GeS₂·35Ga₂S₃·40CsCl:0.3Er glass composition, and discuss the mechanism of enhanced luminescence. By monitoring the ⁴I_9/2–⁴I_15/2 of Er³⁺ transition, up‐conversion luminescence of 12 times higher was observed in glass–ceramics compared with that in base glass. Electron paramagnetic resonance (EPR) and Raman scattering spectroscopies were employed to obtain the information of selective environment of Er³⁺ ions and microstructural evolution with the crystallization progress. Both of them evidenced that the enhanced up‐conversion luminescence was mainly related to the local environmental evolution from a mixed chlorine‐sulfur coordination to a low phonon energy chlorine coordination in the residual glassy matrix of glass–ceramics.     

Spectroscopic and energy transfer mechanism of Er3+, Pr3+-codoped ZBYA glass

Absorption spectra, emission spectra and the rate parameters of the energy-exchange processes relevant to the ⁴I_11/2→⁴I_13/2 laser transition in Er³⁺/Pr³⁺- codoped ZBYA(ZrF₄–BaF₂–AlF₃–YF₃) glass were presented. Intensive 2.7 μm emission was obtained in the codoped glass and the optimized concentration ratio of Pr³⁺ to Er³⁺ was found to be 0.1:1. With the presence of Pr³⁺ ions, the intensities of the green and near-infrared emission were dramatically reduced to 1/15 and 1/21, respectively. The Er³⁺/Pr³⁺-codoped sample was found to have higher predicted spontaneous transition probability (16.57%) along with larger calculated emission cross section (14.6×10⁻²¹ cm²). These results suggest that the 2.7 μm emission of Er³⁺ ions could be achieved in ZBYA glass and codoping with Pr³⁺ could greatly improve the mid-infrared emission performance.     

Experimental and theoretical studies on NIR luminescence of titanate-germanate glasses doped with Pr3+ and Tm3+ ions

Near-infrared (NIR) luminescence of Pr³⁺ and Tm³⁺ ions in titanate-germanate glasses has been studied for laser and fiber amplifier applications. The effect of the molar ratio GeO₂:TiO₂ (from 5:1 to 1:5) on spectroscopic properties of glass systems was studied by absorption, luminescence measurements, and theoretical calculations using the Judd–Ofelt theory. It was found that independent of the TiO₂ concentration, intense NIR emissions at 1.5 and 1.8 μm were observed for glasses doped with Pr³⁺ and Tm³⁺ ions, respectively. Moreover, several spectroscopic and NIR laser parameters for Pr³⁺ and Tm³⁺ ions, such as emission bandwidth, stimulated emission cross-section, quantum efficiency, gain bandwidth, and figure of merit, were determined. The results were discussed in detail and compared to the different laser glasses. Systematic investigations indicate that Pr³⁺-doped system with GeO₂:TiO₂ = 2:1 and Tm³⁺-doped glass with GeO₂:TiO₂ = 1:2 present profit laser parameters and could be successfully applied to NIR lasers and broadband optical amplifiers.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Quantitative prediction of the structure and luminescence properties of Nd3+ doped borate laser glasses

Although great advance has been made in glass science, predicting luminescence properties of laser glass poses a significant challenge for scientists due to the complex relationship between the composition, structure, and properties of the rare earth ions doped laser glasses. The development of high-performance laser glass usually relies on intuition and trial-and-error. Recently, with the proposal of the materials genome engineering, the “glass genome” has also attracted much attention. Here, the structure of the Nd³⁺ doped B₂O₃-Li₂O laser glasses was analyzed using Fourier transform infrared spectra and nuclear magnetic resonance, revealing that the glass contains similar glass-forming ion-centered coordination polyhedron structure groups to the neighbor congruent glassy compounds. The structure and properties of glass largely depend on the neighbor congruent glassy compounds. Therefore, the structure and luminescence properties of Nd³⁺ doped B₂O₃-Li₂O and B₂O₃-MgO-Li₂O laser glasses can be quantitatively predicted via the neighbor congruent glassy compounds. The predictive values are in good agreement with the experimental data, which indicates that our approach is an effective way to predict the structure and luminescence properties of Nd³⁺ doped borate laser glasses.     

Ca2+/Sr2+/Ba2+ dependent phase separation,nanocrystallization and photoluminescence in fluoroaluminosilicate glass

Fluoride phase separation is the initial stage of nanocrystallization in oxyfluoride glasses, and it is a key step in achieving transparent glass-ceramics with good luminescence. In this work, we combine molecular dynamics (MD) simulations and experimental studies to investigate the phase separation, nanocrystallization and photoluminescence in fluoroaluminosilicate glass and glass-ceramics containing alkali earth fluoride (MF₂). The results reveal different phase separation behaviors due to the field strength difference of M²⁺. The composition and size similarity between the fluoride-rich regions in the MD simulated glass and the fluoride nanocrystals in the experimental prepared glass-ceramics are observed, suggesting that the separated fluoride phase is the structural origin of the observed MF₂ nanocrystals. Besides, in order to understand the M²⁺ dependent glass structural features, the crystallization temperatures, the luminescent properties of Eu³⁺ and Eu²⁺ doped glass-ceramics, and the lasing performance of Er³⁺ doped glass-ceramics are discussed. Based on these comprehensions, some strategies are proposed to help to efficiently design oxyfluoride glass with desired luminescence performance.     

Effects of Er3+ and/or Cr3+ doping on crystallization activation energy and fluorescence properties of transparent ZnGa2O4 glass-ceramics

Er³⁺ and/or Cr³⁺ doped transparent ZnGa₂O₄ glass-ceramics were successfully obtained by one-step heat treatment. The results showed that Er³⁺ ions can enrich around ZnGa₂O₄ crystal to reduce the crystallization activation energy and promote the growth of ZnGa₂O₄ crystal. Cr³⁺ ions may successfully occupy the Ga³⁺ sites in the ZnGa₂O₄ lattice but will increase crystallization activation energy and inhibit the growth of the ZnGa₂O₄ crystal. Before and after crystallization, the coordination-field intensity of Cr³⁺ ions increased from 2.17 to 2.86, resulting in the peak position of its emission spectra moving from 850 to 688 nm. By excitation at 378 nm, the precursor glass co-doped with Er³⁺ and Cr³⁺ ions only showed the characteristic emission peaks belonging to Er³⁺ ions. After heat treatment, the characteristic emission peaks belonging to Er³⁺ and Cr³⁺ ions existed simultaneously, and the emission color changed from green to yellow. By excitation at 980 nm, there were only characteristic emission peaks belonging to Er³⁺ ions of the Er³⁺/Cr³⁺ co-doped glasses before and after heat treatment. The results showed that the Er³⁺ and/or Cr³⁺ doped ZnGa₂O₄ glass-ceramics have adjustable luminescence ability and show potential application value in the field of luminescence display.     

Dual-mode optical ratiometric thermometer based on rare earth ions doped perovskite oxides with tunable luminescence

Rare earth ions doped luminescent materials have drawn considerable attention as they can generate both upconversion and downshifting emissions. Here, the rare earth ions Pr³⁺/Er³⁺ codoped perovskite oxide Bi₄Ti₃O₁₂ is proposed as a dual-mode temperature sensor and anti-counterfeiting material based on its up/down-conversion luminescence. Under 481 nm excitation, the intensity ratio of green emission (～523 nm in Er³⁺) and red emission (～611 nm in Pr³⁺) brings about a very high absolute sensitivity (S_a) of 2% K^?1 at 568 K and a maximum relative sensitivity (S_r) of 1.03% K^?1 at 478 K in the temperature range of 298–568 K. In addition, the upconversion green emissions of Er³⁺ yield a relatively-high S_r of 1.1% K^?1 at 298 K with 980 nm excitation, which can provide self-calibration coupled with down-conversion luminescence temperature sensing mode. Besides, this phosphor also shows tunable luminous colors for the potential application in the anti-counterfeiting field under various excitation wavelengths.     

Realizing particle population inversion of 2.7 μm emission in heavy Er3+/Pr3+ co-doped low hydroxyl fluorotellurite glass for mid-infrared laser

In this work, the population bottleneck of Er³⁺: ⁴I_11/2 → ⁴I_13/2 was overcome for the first time in heavy Er³⁺/Pr³⁺ co-doped TeO₂–BaF₂–La₂O₃–LaF₃ (TBLL) low hydroxyl fluorotellurite glasses. Infrared emission spectra and fluorescence lifetime decay curves reveal that Pr³⁺ ions could deplete the electrons from the Er³⁺: ⁴I_13/2 level faster than those from the Er³⁺: ⁴I_11/2 under 980 nm excitation. Specifically, the energy transfer (ET) efficiency of the Er³⁺: ⁴I_13/2 → Pr³⁺: ³F_3,4 process (ET1) reached 96.27%, while that of the Er³⁺: ⁴I_11/2 → Pr³⁺: ¹G₄ process (ET2) is only 2.17% in the Er³⁺/Pr³⁺ co-doped glass. Additionally, the energy transfer mechanism of Er³⁺ and Pr³⁺ ions was investigated using the Dexter theory, where the energy transfer microscopic parameters C_D-A are 13.21 × 10⁻⁴⁰ cm⁶/s and 0.89 × 10⁻⁴⁰ cm⁶/s for the ET1 and ET2 processes, respectively. Finally, a numerical simulations laser model was developed to discuss the laser properties of the Er³⁺/Pr³⁺ co-doped TBLL fibers. The simulation results indicate that a 2.7 μm laser with a maximum output power of 2.26 W and slope efficiency of 13.89% could be achieved when the fiber background loss is reduced to 0.5 dB/m. The above results suggest that the Er³⁺/Pr³⁺ co-doped TBLL glass has great potential applications in mid-infrared fiber lasers.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.     

Analysis of the spectroscopic parameters of chalcogenide glasses in the Ga-Ge-S: Er3+ system

The spectroscopic characteristics of chalcogenide glasses in the Ga-Ge-S: Er³⁺ system are determined. The oscillator strengths, the Judd-Ofelt intensity parameters, the probabilities of spontaneous radiative transitions, and the radiative lifetimes of levels are calculated from the absorption spectroscopy data for two series of Ga-Ge-S chalcogenide glasses doped with Er³⁺ ions. In the first series, the Er₂S₃ content is varied from 0.49 to 4.64 mol % at the fixed composition of the glass matrix (0.15Ga₂S₃ · 0.85GeS₂). In the second series, the Ga₂S₃ content is varied from 10 to 30 mol % at the fixed Er₂S₃ content (1.94 mol %). The aforementioned spectroscopic parameters are analyzed as a function of the chalcogenide glass composition. It is revealed that the values of the oscillator strengths and the probabilities of spontaneous radiative transitions in Er³⁺ ions in the chalcogenide matrix are larger than those in phosphate, germanate, and tellurite matrices.     

Intense broadband 3.1 μm emission in Er3+-doped fluoroaluminate-tellurite glass for mid-infrared laser application

Er³⁺ single doped fluoroaluminate-tellurite glasses were made by employing a conventional melt-quenching technique. A strong fluorescence around 3.1 μm was achieved from Er³⁺-doped fluoride glasses, under a 980 nm laser diode pump, which was assigned to the Er³⁺: ⁴S_3/2 → ⁴F_9/2 radiation transition process. The up-conversion and mid-infrared spectra of emission for fluoroaluminate-tellurite glasses with various concentrations of Er³⁺ ions dopant was researched. In addition, the calculated fluorescence lifetime value about 3.1 μm reaches 0.48 ms. The findings indicate that fluoroaluminate-tellurite glasses doped with Er³⁺ have prospects of being developed into 3.1 μm mid-infrared fiber and laser materials.     

Enhanced near-infrared to green upconversion from Er3+-doped oxyfluoride glass and glass ceramics containing BaGdF5 nanocrystals

In this work, effect of glass composition as well as ceramization on visible and near-infrared (NIR) luminescence properties along with their decay dynamics of Er³⁺ ions has been compared considering two different oxyfluoride glasses yielding BaF₂ and BaGdF₅ nanocrystals. Both the glass systems have exhibited an intense normal and upconversion green emission under ultraviolet (378 nm) and NIR (978 nm) excitations, respectively. A remarkable enhancement of these emission intensities is observed for gadolinium-(Gd) containing glasses. Interestingly, NIR fluorescence intensity from Er³⁺ ions at 1540 nm has showed marginal decrease in gadolinium-containing glass which is attributed to occurrence of strong excited-state absorption (ESA) due to higher fluorine content ensuing an augmentation of upconversion green emission with a concomitant decrease in NIR emission. The quadratic dependence of upconversion green emission intensity on its pump power for all the samples revealed biphotonic absorption process from ground-state ⁴I_15/2 to the excited-state ⁴I_11/2 followed by ESA of second photon to the ⁴F_7/2 level. The intense green upconversion emission as well as enhanced NIR fluorescence lifetimes indicate the suitability of these glass/glass ceramics for upconversion lasers and amplification in the third telecom window.     

Photoluminescence Properties of Er/Pr‐Doped K0.5Na0.5NbO3 Ferroelectric Ceramics

Er/Pr‐doped K_0.5Na_0.5NbO₃ ceramics have been fabricated and the effects of Pr³⁺ on their photoluminescence properties have been investigated systematically. The visible upconversion emissions, near‐infrared and mid‐infrared downconversion emissions of Er³⁺ ions under the excitation of 980 nm have been studied in detail. The effects of Pr³⁺ on PL properties and energy‐transfer processes have also been elucidated. By selecting an appropriate excitation source, simultaneous visible downconversion emissions of Er³⁺ and Pr³⁺ ions can be realized, and the emission colors of the ceramics can be tuned via the concentration of Pr³⁺ ions in a wide range from yellowish green to yellow. Our results also reveal that the photoluminescence emissions of the ceramics can be enhanced by the alignment of polarization of the ferroelectric host.     

Effect of ligand field symmetry on upconversion luminescence in heat‐treated LaBGeO5:Yb3+, Er3+ glass

In this paper, we report upconversion (UC) luminescence enhancement in LaBGeO₅:Yb³⁺, Er³⁺ glass‐ceramics (GCs), surface crystallized glass‐ceramics (SCGCs) and ceramics compared with the as‐melt glass fabricated by the conventional melt‐quenching technique. Based on structural investigations, we find that the nucleation and crystallization of trigonal stillwellite LaBGeO₅:Yb³⁺, Er³⁺ nanocrystals occur first at the glass surface before the following volume crystallization. The local site symmetry around rare earth (RE) ions which was evaluated using the Eu³⁺ ions as a probe together with Judd‐Ofelt theory calculations exhibits a clear increase with the devitrification of the glass. Consequently, complete crystallization of the glass leads to largest enhancement in the UC emissions of the LaBGeO₅:Yb³⁺, Er³⁺ ceramics. We ascribe the enhancement of UC luminescence in the LaBGeO₅:Yb³⁺, Er³⁺ GCs, SCGCs, and ceramics to the structural ordering and the improvement of site symmetry surrounding RE ions that minimizes the rate of nonradiative relaxation process.     

Ce3+‐ and Dy3+‐Doped Oxyfluoride Borosilicate Glasses with Near White Luminescence

A series of Ce³⁺/Dy³⁺‐doped oxyfluoride borosilicate glasses prepared by melt‐quenching method are investigated for light‐emitting diodes applications. These glasses are studied via X‐ray diffraction (XRD), optical absorption, photoluminescence (PL), color coordinate, and Fourier transform infrared (FT‐IR) spectra. We find that the absorption and emission bands of Ce³⁺ ions move to the longer wavelengths with increasing Ce³⁺ concentrations and decreasing B₂O₃ and Al₂O₃ contents in the glass compositions. We also discover the emission behavior of Ce³⁺ ions is dependent on the excitation wavelengths. The glass structure variations with changing glass compositions are examined using the FT‐IR spectra. The influence of glass network structure on the luminescence of Ce³⁺/Dy³⁺ codoped glasses is studied. Furthermore, the near‐ideal white light emission (color coordinate x = 0.32, y = 0.32) from the Ce³⁺/Dy³⁺ codoped glasses excited at 350 nm UV light is realized.