First Identification of Rare‐Earth Oxide Nucleation in Chalcogenide Glasses and Implications for Fabrication of Mid‐Infrared Active Fibers

Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy³⁺‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge_16.5As_(19?x)Ga_xSe_64.5 (at.%), for x = 3 and 10, named Ga₃ and Ga₁₀ glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga₂Se₃. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy₂O₃ is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.     

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.     

Optical Property of Dy3+‐and Ce3+‐Doped Si–B–Na–Sr Glasses

Novel Dy³⁺ and Ce³⁺ doped Si–B–Na–Sr (SBNS) glasses were synthesized by melt‐quenching technique. Excited by 327 nm, the 0.5Dy³⁺‐and 0.5Ce³⁺‐doped SBNS exhibits white emission with Commission Internationale de L'Eclairage coordinates of (0.308, 0.280). Basic optical characterizations have been performed by measuring the absorption and emission spectra and calculating Judd–Ofelt intensity parameters, radiative probability, luminescence branching ratio, cross sections, and effective bandwidth. The Judd–Ofelt parameters Ω₂, Ω₄, and Ω₆ indicate a high asymmetrical environment and covalent environment in the optical glass. The emission color of Ce³⁺ and Dy³⁺ codoped transparent glass can be tuned from blue to white through energy transfer from Ce³⁺ to Dy³⁺ ions. The resulting glass may have potential application in white‐light‐emitting source.     

Eu‐, Tb‐, and Dy‐Doped Oxyfluoride Silicate Glasses for LED Applications

Luminescence glass is a potential candidate for the light‐emitting diodes (LEDs) applications. Here, we study the structural and optical properties of the Eu‐, Tb‐, and Dy‐doped oxyfluoride silicate glasses for LEDs by means of X‐ray diffraction, photoluminescence spectra, Commission Internationale de L'Eclairage (CIE) chromaticity coordinates, and correlated color temperatures (CCTs). The results show that the white light emission can be achieved in Eu/Tb/Dy codoped oxyfluoride silicate glasses under excitation by near‐ultraviolet light due to the simultaneous generation of blue, green, yellow, and red‐light wavelengths from Tb, Dy, and Eu ions. The optical performances can be tuned by varying the glass composition and excitation wavelength. Furthermore, we observed a remarkable emission spectral change for the Tb³⁺ single‐doped oxyfluoride silicate glasses. The ⁵D₃ emission of Tb³⁺ can be suppressed by introducing B₂O₃ into the glass. The conversion of Eu³⁺ to Eu²⁺ takes place in Eu single‐doped oxyfluoride aluminosilicate glasses. The creation of CaF₂ crystals enhances the conversion efficiency. In addition, energy transfers from Dy³⁺ to Tb³⁺ and Tb³⁺ to Eu³⁺ ions occurred in Eu/Tb/Dy codoped glasses, which can be confirmed by analyzing fluorescence spectra and energy level diagrams.     

Ga2S3‐Sb2S3‐CsI chalcohalide glasses for mid‐infrared applications

In this study, a new chalcohalide glass system, Ga₂S₃‐Sb₂S₃‐CsI, is reported. It has a glass‐forming domain composed of ~0‐35 mol% Ga₂S_3, ~15‐95 mol% Sb₂S₃, and ~0‐55 mol% CsI. The glasses have a wide transparent window of ~0.7‐13.5 μm, high third‐order nonlinear refractive indices of ~1.7‐8.7×10^?14 cm²/W @ 1.55 μm, and relatively short zero group‐velocity‐dispersion wavelengths of 3.8‐5.15 μm. The glasses can dissolve more than 2 mol% active ions (e.g., Dy³⁺), and the doped glasses show intense emissions in the mid‐infrared. These superior properties demonstrate their good potentials for mid‐infrared applications such as thermal imaging, nonlinear photonics and lasers.     

Effect of residual chlorine on fluorescence emission of Dy3+ doped chalcogenide glasses with low gallium content

Chlorine or chlorides are usually used as a dehydrating agent for removing the O-H or S(Se)-H in the preparation of high-purity chalcogenide glasses. However, the residual chlorine in some rare-earth ions doped chalcogenide glasses was found to have a great negative impact on fluorescence emission. In this work, the effect of residual chlorine on the fluorescence emission of Dy³⁺ ions in serial (Ge)GaAsSbS glasses was studied quantitatively, and the reasons were discussed. Cl₂ gas and SbCl₃ were used as the source of chlorine and their residual contents were controlled by the post-distillation process and added content, respectively. The results can give some suggestions for how to eliminate the negative effects of chlorine and improve the glass’ optical gain properties.     

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.     

Compositional dependence of the optical properties of novel Ga–Sb–S–XI (XI = PbI2, CsI,AgI) infrared chalcogenide glasses

A novel family of Ga₂S₃–Sb₂S₃–XI (XI = PbI₂, CsI, AgI) was investigated to understand the role of metal halides and exploit new chalco‐halide glasses for infrared optics. The dependence of the thermal properties, infrared optical properties, and structural information of the novel family on different metal–iodines was investigated. Results showed that metal halides increase the glass stability but decrease the glass network connectivity. The compositional dependence of the short‐wave cut‐off edge is associated with the electronegativity difference between the cations and anions of the metal halides. Raman study showed that the metal–iodine modified the glass structure mainly through the iodide content, and the cations dissolved in the glass network mostly as charge compensators for the aperiodic network. For the glasses in the series Ga₂S₃–Sb₂S₃–XI–Dy³⁺, Dy³⁺ emission increased in the PbI₂‐ and CsI‐doped glasses but decreased in the AgI‐doped glass due to the combined effect of dysprosium and oxygen. For all that, these novel glasses are highly promised for use in infrared optics.     

Tunable colors and applications of Dy3+/Eu3+ co-doped CaO-B2O3-SiO2 glasses

A series of Dy³⁺/Eu³⁺ single- and co-doped calcium borosilicate luminescent glasses were prepared by the conventional high temperature melt-quenching method. A compact glass structure is obtained by the addition of Dy³⁺/Eu³⁺ ions, which is verified by the physical properties of synthetic glasses. As network modifiers, Dy³⁺/Eu³⁺ fill in the interspaces of glass network and contribute to the conversion of [BO₃] to [BO₄]. Dy³⁺/Eu³⁺ co-doped calcium borosilicate glasses can emit white light, which consists of blue, yellow, and red light under 387 nm excitation. The emission spectra and decay curves of the white-emitting glasses have proved the existence of energy transfer. The average lifetime of Dy³⁺ decreases from 0.251 to 0.165 ms with the increasing Eu³⁺ concentration. Changing rare earth ions concentration, CIE color coordinates of Dy³⁺/Eu³⁺ co-doped glass shifts from cyan to white with increasing excitation wavelength. A white-light emission is obtained when the concentration of Dy³⁺ and Eu³⁺ equals to 4% and 2%, respectively. Moreover, the Dy³⁺/Eu³⁺ co-doped calcium borosilicate glass shows high-thermal stability and it may be applicable for high-quality white LEDs based on high power near ultraviolet (n-UV) LED chip in the future.     

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.     

Nanoscale mechanism of rare‐earth doping in Ga‐codoped glassy As‐Sb selenides

The method of annihilating positrons in positron annihilation lifetime measuring mode is applied to study mechanism of rare‐earth doping in Ga‐codoped arsenic selenide As₂Se₃ glass modified with Sb. The atomic‐deficient structure of parent As₂Se₃ glass is imagined as containing positron‐trapping sites in the form of free‐volume voids within cycle‐type arrangement of corner‐sharing trigonal AsSe_3/2 pyramids, composed of atomic‐accessible geometrical holes arrested by surrounding atomic‐inaccessible Se‐based bond‐free solid angles. The Ga codoping in As₂Se₃ glass causes gradual decrease in trapping rate and fraction of trapped positrons due to agglomeration of free‐volume voids. Partial As‐to‐Sb replacement in Ga‐codoped As‐Se glasses leads to better stability against crystallization processes and possibility to further rare‐earth doping without principal changes in the type of positron‐trapping defects. Effect of 500 wppm of Pr³⁺ in Ga₂(As_0.28Sb_0.12Se_0.60)₉₈ glass is explained in terms of competitive contribution of changed occupancy sites in Ga‐modified glassy network available for rare‐earth ions and annihilating positrons.     

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.     

The influence of different antimony content in Ga-As-Sb-S chalcogenide glass system: Modification of physical & spectroscopic properties and fiber forming ability

In order to improve the fiber drawing performances including the anti-crystallization in fiber drawing process and the mechanical properties, the fourth component of antimony (Sb) was introduced into Ga_0.8As_39.2S₆₀ glass, and a serial Ga_0.8As_39.2-xSb_xS₆₀ (x = 0, 1, 3,5, 7, 9 and 11) novel chalcogenide glasses doped with 3000 ppmw Dy³⁺ ions were prepared. The influences of antimony content on the physical properties, spectroscopic properties and fiber forming ability of glass were investigated. The experiment results indicate that the introduction of moderate antimony into glass effectively improves the fiber drawing performance and the spectroscopic properties of Dy³⁺ ions. The Ga_0.8As_34.2Sb₅S₆₀ composition glass possesses the best performance and it is recommended a good candidate for mid-infrared laser working medium.     

Structured active fiber fabrication and characterization of a chemically high-purified Dy3+-doped chalcogenide glass

By conventional melt-quenching techniques, a series of Dy³⁺-doped (0.1 to 1.0 wt%) Ga₅Ge₂₀Sb₁₅S₆₀ bulk glasses were fabricated and their potential for developing mid-infrared fiber laser beyond 4 μm were evaluated, in which the optimal Dy³⁺ doping concentration was found to be 0.3 wt% and the largest laser quality factor value (σ_e × τ_mea = 2.62 × 10⁻²³ cm² s) among all of the Dy³⁺-doped chalcogenide glass was obtained. On this basis, through using the chemical purification methods with chlorine gas combined with the dynamic distillation process, the high-purity GGSS glasses with low O–H and S–H absorptions were successfully fabricated, which was confirmed by the optimized mid-infrared linear transmittance and improved fluorescent lifetimes of Dy³⁺: ⁶H_13/2, ⁶H_11/2 levels. Furthermore, for the first time to the best of our knowledge, the Dy³⁺-doped, single-mode, and double-cladding chalcogenide fibers with the core/cladding ratios of 125:60:11 and 125:66:11.5 were achieved by a multistage rod-in-tube fiber drawing process and extrusion methods, respectively. The GeS₂-based fiber exhibits excellent transmission performance at 1.0-5.0 μm: 3.0 dB/m at 2.9 μm (O–H), 2.4 dB/m at 4.1 μm (S–H). Combining the advantages of high-purity, high doping concentration and single-mode double-cladding structure, the optimized active fiber should be an ideal efficient and low-threshold medium toward mid-infrared fiber laser beyond 4 μm.     

Synthesis and luminescence properties of single‐component Ca5(PO4)3F:Dy3+, Eu3+ white‐emitting phosphors

A series of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors was synthesized by a solid‐state reaction method. The XRD results show that all as‐prepared Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ samples match well with the standard Ca₅(PO₄)₃F structure and the doped Dy³⁺ and Eu³⁺ ions have no effect on the crystal structure. Under near‐ultraviolet excitation, Dy³⁺ doped Ca₅(PO₄)₃F phosphor shows blue (486 nm) and yellow (579 nm) emissions, which correspond to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions respectively. Eu³⁺ co‐doped Ca₅(PO₄)₃F:Dy³⁺ phosphor shows the additional red emission of Eu³⁺ at 631 nm, and an improved color rendering index. The chromaticity coordinates of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors also indicate the excellent warm white emission characteristics and low correlated color temperature. Overall, these results suggest that the Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors have potential applications in warm white light‐emitting diodes as single‐component phosphor.     

Structural insights in Dy3+‐doped β‐Tricalcium phosphate and its multimodal imaging characteristics

A series of Dysprosium (Dy³⁺) doped β‐Tricalcium phosphate [β‐TCP, β‐Ca₃(PO₄)₂] were developed for applications in magnetic resonance imaging (MRI) and computed tomography (CT). Characterization studies confirmed the Dy³⁺ occupancy at Ca²⁺(1), Ca²⁺(2), and Ca²⁺(3) lattice sites of β‐Ca₃(PO₄)₂ and its substitution limit was determined as 4.35 mol%. The transitions from the ⁶H_15/2 ground state to various excited energy levels is validated by the characteristic absorption peaks of Dy³⁺. Luminescence studies inferred two intense bands at 480 and 572 nm due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions of Dy³⁺. The paramagnetic and nontoxic behavior of Dy³⁺‐doped β‐Ca₃(PO₄)₂ were confirmed from magnetic and MTT tests, respectively. Dy³⁺ in the host induces a high X‐ray absorption ability for X‐ray computed tomography (CT) and showed efficient contrast T₂‐enhancing modality. Thus the proposed system could be used as a promising probe for multimodality with optical imaging, computed tomography and magnetic resonance imaging.     

Bright White‐Emitting Phosphors Ba2Gd(BO3)2Cl: Dy3+/Dy3+‐Tm3+ for Hg‐Free Lamps and White LEDs Applications

Spectroscopic properties of Ba₂Gd(BO₃)₂Cl: Dy³⁺ and Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ under vacuum ultraviolet (VUV) and ultraviolet (UV) light excitations were investigated. Dy³⁺ single‐doped Ba₂Gd(BO₃)₂Cl showed broad absorption band in the VUV region, and bright warm white light with chromaticity coordinates (CIE) of (0.340, 0.381) upon VUV excitation at 172 nm, demonstrating this phosphor's applicability in mercury free lamps. Upon direct excitation Tm³⁺ from its ⁶F₆ level to ¹D₂ level, the decrease of emission intensity and lifetime of Tm^{3+ 1}D₂–³F₄ emission with increasing concentration of Dy³⁺ in Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ confirmed the occurrence of energy transfer from Tm³⁺ to Dy³⁺. In addition, Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ could be efficiently excited by 358 nm UV light and its emission color could be tuned from blue to yellow by codoping Tm³⁺. When 1% Tm³⁺ and 5% Dy³⁺ were codoped in the Ba₂Gd(BO₃)₂Cl, intensive white‐emitting light with CIE of (0.352, 0.328) and correlated color temperature of 4589 K was achieved upon 358 nm excitation, revealing the potential application of Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ for white light‐emitting diodes (LEDs).     

Why is it so difficult to realize Dy4+ in as-synthesized BaZrO3?

Rare-earth doped barium zirconate (BaZrO₃) ceramics are of interest as proton-conducting and luminescent materials. Here, we report a study of dysprosium (Dy) and other relevant point defects in BaZrO₃ using hybrid density-functional defect calculations. The tetravalent Dy⁴⁺ is found to be structurally and electronically stable at the Zr lattice site (i.e., as Dy_Zr⁰), but most often energetically less favorable than the trivalent Dy³⁺ (i.e., Dy_Zr^–) in as-synthesized BaZrO₃, due to the formation of low-energy, positively charged oxygen vacancies and the mixed-site occupancy of Dy in the host lattice. The Dy⁴⁺/Dy³⁺ ratio can, in principle, be increased by preparing the material under highly oxidizing and Ba-rich conditions and co-doping with acceptor-like impurities; however, a post-synthesis treatment may still be needed to realize a nonnegligible Dy⁴⁺ concentration. We also find that certain unoccupied Dy 4f states and the O 2p states in the Dy_Zr⁰ configuration are strongly hybridized, a feature not often seen in rare-earth-containing materials, and that the isolated Dy_Zr defect might be the source of a broad blue emission in band-to-defect (“charge-transfer”) luminescence.     

Uniform Coating of BaTiO3–Dy2O3–SiO2 Compound Nano Layer on Ni Particles for MLCC Electrode

Uniform coating of nanometer‐scale BaTiO₃–Dy₂O₃–SiO₂ layers on spherical Ni particles are achieved by controlled hydrolysis of tetrabutyl titanate (TBT), hydrothermal reaction with Ba(OH)₂, and co‐precipitation of tetraethylorthosilicate (TEOS) and Dy(NO₃)₃. The composition of the coating layer is similar to rare earth oxide‐silica–doped BaTiO₃, which is the main component of dielectric layer for base metal electrode (BME) multilayer ceramic capacitors (MLCCs). After coating, the shrinkage onset temperature of Ni particles is significantly increased. After sintered to pellets, the electrode has good electrical conductivity. This electrode material has good compatibility with rare earth oxide and silica‐doped BaTiO₃ dielectric materials, and could serve as promising candidate for application in the next generation BME‐MLCCs.     

Dy and Eu activated Ca3B2O6 phosphors for near ultraviolet‐based light‐emitting diodes

The Dy‐ and Eu‐activated Ca₃B₂O₆ phosphors were synthesized by a high‐temperature solid‐state reaction technique and their structural and luminescent properties were investigated. The phosphors are characterized by X‐ray diffraction, photoluminescence spectra, and Commission International de I'Eclairage (CIE) chromaticity coordinates. It is found that the charge compensator Na⁺ plays an important role in modifying the emission spectral profiles of Dy and Eu ions in the phosphors. The ratio of the emission located at the yellow wavelength portion to that located at the blue wavelength region of the Dy³⁺ ions can be apparently tuned by changing the Na⁺ content. The luminescence intensity of the phosphors can be enhanced with introducing Na⁺ ions as well. The emission colors of Dy/Eu codoped phosphors change from blue to white and successfully acquire the superior white light emission (x = 0.330, y = 0.329) by appropriately tuning the Na⁺/Dy³⁺ content and the excitation wavelength. The energy transfer process from Eu²⁺ to Dy³⁺ and Eu³⁺ occurs in the Dy/Eu codoped phosphors, providing a further approach to modify the emission spectral profile of the examined phosphors. The phosphors presented here have promising applications in the fields of light‐emitting diodes.