Fabrication and Characterization of Glass‐Ceramic Fiber‐Containing Cr3 + ‐Doped ZnAl2O4 Nanocrystals

Glass‐ceramic fibers containing Cr³⁺‐doped ZnAl₂O₄ nanocrystals were fabricated by the melt‐in‐tube method and successive heat treatment. The obtained fibers were characterized by electro‐probe micro‐analyzer, X‐ray diffraction, Raman spectrum and high‐resolution transmission electron microscopy. In our process, fibers were precursor at the drawing temperature where the fiber core glass was melted while the clad was softened. No obvious element interdiffusion between the core and the clad section or crystallization was observed in precursor fiber. After heat treatment, ZnAl₂O₄ nanocrystals with diameters ranging from 1.0 to 6.3 nm were precipitated in the fiber core. In comparison to precursor fiber, the glass‐ceramic fiber exhibits broadband emission from Cr³⁺ when excited at 532 nm, making Cr³⁺‐doped glass‐ceramic fiber a promising material for broadband tunable fiber laser. Furthermore, the melt‐in‐tube method demonstrated here may open a new gate toward the fabrication of novel glass‐ceramic fibers.     

Enhanced broadband NIR emission in glass–ceramic fibers containing Nd3+/Yb3+ co-doped YCa4O(BO3)3 disordered nanocrystal

Demands are increasing for ultrashort pulse laser in industrial applications, where the gain bandwidth of most optical fiber material is not wide enough, and developing a wide bandwidth gain medium is challenging. Glass–ceramic fibers containing Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were fabricated by the molten core method and successive heat treatment. After a careful heat treatment, Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were precipitated in the fiber core. Enhanced broadband near-infrared (NIR) emission from 850 to 1150 nm (bandwidth: ∼252 nm) was obtained in the glass–ceramic fiber compared to that of precursor fiber. These results suggest that the Nd³⁺/Yb³⁺ glass–ceramic fibers are promising for broadband NIR optical amplifications and lasers.     

Nd3+/Sm3+ codoped NaLa(WO4)2 glass ceramic: A novel optical heater

Transparent Nd³⁺/Sm³⁺ codoped tungstate silicate glass ceramics were prepared and used for the photothermal conversion process. XRD patterns, TEM image and the enhanced Raman signals confirm the appearance of the tetragonal scheelite NaLa(WO₄)₂ nanocrystals in the vitreous phase. In comparison to the precursor glass, the enhancement of photoluminescence of Nd³⁺ ions in the glass ceramics attributes to the enrichment of Nd³⁺ ion in the precipitated low phonon-energy tetragonal scheelite NaLa(WO₄)₂ nanocrystals. The rapid reduction of photoluminescence of Nd³⁺ ions in the Nd³⁺/Sm³⁺ codoped glass ceramics demonstrates that a strong energy transfer from Nd³⁺ to Sm³⁺ takes place, which provides more non-radiative relaxation channels and is beneficial for the improving the photothermal conversion efficiency. Under the irradiation of 808 nm laser diode, a significant temperature rise is observed in the Nd³⁺/Sm³⁺ codoped glass ceramics and may be used as a good optical heater.     

Near-infrared long-lasting phosphorescence in transparent glass ceramics embedding Cr3+-doped LiGa5O8 nanocrystals

Cr³⁺ doped transparent glass ceramics of SiO₂–Ga₂O₃–Li₂O were fabricated by melt-quenching and subsequent crystallization. X-ray diffraction and transmission electron microscopy analyses evidenced that cubic LiGa₅O₈ nanocrystals were homogeneously precipitated among the silicate glass matrix. The incorporation of Cr³⁺ ions into LiGa₅O₈ nanocrystals was evidenced by absorption, emission and time-resolved luminescence spectra. Impressively, the present Cr³⁺ doped glass ceramics were demonstrated to be a new near-infrared (∼720 nm) long-lasting bulk phosphor whose luminescence can last for more than 2 h after stoppage of UV (250–350 nm) irradiation. The occurring of Cr³⁺ long-lasting phosphorescence in the glass ceramics was confirmed to be mainly due to the precipitation of Cr³⁺:LiGa₅O₈ nanocrystals from glass matrix. The filling/releasing of electrons into/from the intrinsic traps of LiGa₅O₈ nanocrystals through the conduction band of host were proposed to be responsible for the realization of the long-lasting phosphorescence of the investigated Cr³⁺ doped glass ceramics.     

Structure and optical properties of transparent Er3+-doped CaF2–silica glass ceramic prepared by controllable sol–gel method

Transparent Er³⁺-doped CaF₂–silica glass ceramics were prepared by the direct physical introduction of Er³⁺ doped CaF₂ nanocrystals into acid-catalyzed sol–gel silica glass. The physical methods of ball milling, ultrasonic baths, and stirring were investigated to disperse Er³⁺ doped CaF₂ nanocrystals in the silica sols. The CaF₂–silica sol mixture went through gelation and heat-treatment to form Er³⁺-doped CaF₂–silica glass ceramics. The morphology of Er³⁺ doped CaF₂ in silica glass did not change after heat-treatment at 600 °C for 10 h. The experimental results showed that Er³⁺ doped CaF₂ in the glass ceramic prepared with the assistance of ball milling possesses the best dispersity and homogeneity. The highest in-line transmittance of the glass ceramic reached up to 85% in visible region. Glass ceramic exhibits efficient up-conversion emissions corresponding to the Er³⁺:⁴F_9/2→⁴I_15/2 transition and long lifetime of ⁴F_9/2 level (1.73 ms) under 980 nm excitation.     

Structure and luminescence properties of Eu3+ doped TiO2 nanocrystals and prolate nanospheroids synthesized by the hydrothermal processing

We report on a new approach to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids. They were synthesized by shape transformation of hydrothermally treated titania nanotubes at different pH and in the presence of Eu³⁺ ions. The use of nanotubes as a precursor to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids opens the possibility of overcoming the problems related to molecular precursors. The shapes and sizes of the nanotubes, Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids were characterized by transmission electron microscopy (TEM) technique. Crystal structures of the resultant powders were investigated by X-ray diffraction (XRD) analysis. The percentage ratio of Eu³⁺ to Ti⁴⁺ ions in doped nanocrystals was determined using inductively coupled plasma atomic emission spectroscopy. The optical characterization was done by using fluorescence and ultraviolet-visible reflection spectroscopies. An average size of faceted Eu³⁺ doped TiO₂ nanocrystals was 13 nm. The lateral dimensions of Eu³⁺ doped TiO₂ prolate nanospheroids varied from 14 to 20 nm, while the length varied from 40 to 80 nm, depending on precursor concentrations. The XRD patterns revealed the homogeneous anatase crystal phase of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids independently of the amount of dopant. A postsynthetic treatment (filtration or dialysis) was applied on the dispersions of the doped nanoparticles in order to study the influence of the dopant position on photoluminescence (PL) spectra. In the red spectral region, room temperature PL signals associated with ⁵D₀ → ⁷F_J (J = 1–4) transitions of Eu³⁺ were observed in all samples. The increased contribution of dopants from the interior region of dialyzed nanocrystals to photoluminescence was confirmed by the increase of R value.     

Spectral Properties of Pr3+‐Doped Transparent‐Glass‐Ceramic Containing Ca5(PO4)3F Nanocrystals

A Pr³⁺‐doped transparent oxyfluoride glass‐ceramic containing Ca₅(PO₄)₃F nanocrystals was prepared by melt quenching and subsequent thermal treatment. The crystallization phase and morphology of the Ca₅(PO₄)₃F nanocrystals were investigated by X‐ray diffraction and transmission electron microscope, respectively. The volume fraction of the Ca₅(PO₄)₃F nanocrystals in the glass‐ceramic is about 10% and the fraction of Pr³⁺ ions incorporated into the Ca₅(PO₄)₃F nanocrystals is about 22%. The peak absorption cross sections at 435 and 574 nm increase up to 128% and 132% after crystallization, respectively. The peak stimulated emission cross sections of the ³P₀→³H₄ blue laser channel and ³P₀→³F₂ red laser channel for the glass‐ceramic are 4.95 × 10^?20 and 29.8 × 10^?20 cm², respectively. The spectral properties indicate that the glass‐ceramic is a potential visible laser material.     

Thermal,Structural, and Enhanced Photoluminescence Properties of Eu3+‐doped Transparent Willemite Glass–Ceramic Nanocomposites

The precursor glass in the ZnO–Al₂O₃–B₂O₃–SiO₂ (ZABS) system doped with Eu₂O₃ was prepared by the melt‐quench technique. The transparent willemite, Zn₂SiO₄ (ZS) glass–ceramic nanocomposites were derived from this precursor glass by a controlled crystallization process. The formation of willemite crystal phase, size, and morphology with increase in heat‐treatment time was examined by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) techniques. The average calculated crystallite size obtained from XRD is found to be in the range 18–70 nm whereas the grain size observed in FESEM is 50–250 nm. The refractive index value is decreased with increase in heat‐treatment time which is caused by the partial replacement of ZnO₄ units of ZS nanocrystals by AlO₄ units due to generation of vacancies. Fourier transform infrared (FTIR) reflection spectroscopy was used to evaluate its structural evolution. Vickers hardness study indicates marked improvement of hardness in the resultant glass‐ceramics compared with its precursor glass. The photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀→⁷F_j (j = 0, 1, 2, 3, and 4) and its excitation spectra show an intense absorption band at 395 nm. These spectra reveal that the luminescence performance of the glass–ceramic nanocomposites is enhanced up to 17‐fold with the process of heat treatment. This enhancement is caused by partitioning of Eu³⁺ ions into glassy phase instead of into the willemite crystals with progress of heat treatment. Such luminescent glass–ceramic nanocomposites are expected to find potential applications in solid‐state red lasers, phosphors, and optical display systems.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Boroaluminosilicate glass-ceramics containing mullite-type Cr3+:Al4B2O9 nanocrystals with broadband near-infrared luminescence

Multi-component silicate glass is an ideal matrix for fabricating glass-ceramics because of its excellent physical-chemical stability and high optical transmittance. In this paper, a series of Cr³⁺ doped multi-component silicate glasses were designed for the preparation of glass-ceramics that crystalizes mullite-type Cr³⁺:Al₄B₂O₉ nanocrystals. When excited at 450 nm, the obtained GCs exhibit a broadband NIR luminescence band covering a spectral region from 650 to 1200 nm. Two different crystallographic sites of Cr³⁺ in Al₄B₂O₉ nanocrystal are considered to account for the observed broadband luminescence. Due to the controllable size and uniformly dispersion of precipitated nanoparticles, this boroaluminosilicate glass-ceramic could find potential applications as monolithic near-infrared light sources in solid-state light emitting devices.     

Selective excitation in transparent oxyfluoride glass-ceramics doped with Nd3+

Transparent oxyfluoride nano-glass-ceramics have been prepared by melting-quenching and doped with five different Nd³⁺ concentrations (0.1–2 mol%) to obtain the most efficient ⁴F_3/2 → ⁴I_11/2,13/2 emission. It was observed by differential thermal analysis (DTA) that the addition of Nd³⁺ does not affect the crystallization mechanism which corresponds to a diffusion-controlled volumetric process that starts from a constant number of nuclei. Nevertheless, the presence of the dopant affects the kinetics due to the progressive increase of T_g on increasing the Nd³⁺ content. LaF₃ crystals with a size between 9 and 12 nm are obtained after heat treatments at T_g + 20–80 °C as confirmed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HR-TEM). Energy dispersive X-ray (EDX) analysis shows the incorporation of Nd³⁺ ions into the LaF₃ nano-crystals. Judd-Ofelt analysis from the absorption spectra further demonstrate the incorporation of Nd³⁺ ions into the fluoride phase and the most relevant parameters such as radiative lifetime and stimulated emission cross-section are calculated. A detailed optical characterisation clearly shows that Nd³⁺ ions in the glass-ceramics are incorporated in both crystalline and amorphous phases. Low temperature site-selective emission and excitation spectra, together with the different lifetime values of the ⁴F_3/2 state depending on the excitation and emission wavelengths, allow emission from Nd³⁺ ions in the LaF₃ nanocrystals to be identified and correlated with the structural properties. As the Nd³⁺ concentration is increased beyond 0.1 mol%, a stronger quenching of lifetime is observed for Nd³⁺ ions residing in LaF₃ crystals than for those dispersed in the glass matrix. This strong concentration quenching is explained by the much higher concentration of Nd³⁺ ions in the crystalline phase with respect to that in the glass matrix.     

Fabrication and Luminescence Properties of Transparent Glass‐Ceramics Containing Eu3+‐Doped TbPO4 Nanocrystals

Eu³⁺‐doped transparent phosphate precursor glasses and glass‐ceramics containing TbPO₄ nanocrystals were successfully fabricated by a conventional high‐temperature melt‐quenching technique for the first time. The formation of TbPO₄ nanocrystals was identified through X‐ray diffraction, transmission electron microscopy, high‐resolution transmission electron microscopy, selected‐area electron diffraction, and photoluminescence emission spectra. The obvious Stark splitting of ⁵D₀‐⁷F_J (J = 1, 2, 4) transitions of Eu³⁺and the increase of internal quantum efficiency indicate the incorporation of Eu³⁺ into TbPO₄ nanocrystals. Energy transfer from Tb³⁺ ions to Eu³⁺ ions was investigated using excitation and emission spectra at room temperature. The glass‐ceramics obtained have more efficient Tb³⁺ to Eu³⁺ energy transfer than the glass, and so serve as good hosts for luminescent materials.     

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.     

Crystallization control in Ni2+-doped glass-ceramics for broadband near-infrared luminesce

The research of doped photonic glass has recently attracted much attention owning to the significant applications in various fields, including lasers, photovoltaics, and optical amplification. In this work, we present the design, fabrication, and experimental implementation of a novel fluorosilicate photonic glass-ceramics with broadband luminescence. We demonstrate that precipitated nanocrystals can be tuned by changing the heat-treatment temperature. This proposal offers an excellent opportunity for controlling the local environment around Ni²⁺ dopant. Consequently, the broadband and flat emission covering a waveband from 1200 to 2400 nm with a bandwidth of 605 nm can be realized. The possible physical mechanism, which can be attributed to the gradual change of nanocrystals from K₂SiF₆ to KCdF₃ with the enhancement of the heat-treatment temperature, is also discussed.     

Energy transfer,tunable emission and optical thermometry in Tb3+/Eu3+ co-doped transparent NaCaPO4 glass ceramics

Tb³⁺/Eu³⁺ co-doped glass ceramics containing NaCaPO₄ nanocrystals were successfully synthesized via traditional melt-quenching route with further heat-treatment and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy. The energy transfer process of Tb³⁺→Eu³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results indicated that the efficient emission of Eu³⁺ was sensitized by Tb³⁺ under the excitation of 378 nm, realizing tunable emission in the transparent bulk glass ceramics containing NaCaPO₄ nanocrystals. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺:⁵D₄→⁷F₅ (~542 nm) and Eu³⁺:⁵D₀→⁷F₂ (~612 nm). The maximum absolute sensitivity of 4.55% K⁻¹ at 293 K and the maximal relative sensitivity of 0.66% K⁻¹ at T=573 K for Tb³⁺/Eu³⁺ co-doped transparent NaCaPO₄ glass ceramic are obtained. It is expected that the investigated transparent NaCaPO₄ glass ceramics doped with Tb³⁺/Eu³⁺ have prospective applications in display technology and optical thermometry.     

Enhanced near-infrared emission in Yb3+-Cr3+ codoped KZnF3 glass ceramics excited by a solar simulator

Cr³⁺-Yb³⁺ codoped bulk glass-ceramics containing KZnF₃ nanocrystals are fabricated by thermal treatment of cast glass samples and characterized by X-ray diffraction and transmission electron microscopy. The luminescent properties of the glass and glass ceramic are investigated from the measured photoluminescence spectra and fluorescent lifetime. The measurement results demonstrate that Cr³⁺ and Yb³⁺ ions are both predominantly hosted in the KZnF₃ nanocrystals, and the energy absorbed by Cr³⁺ ions is efficiently transferred to Yb³⁺ ions when excited at 450?nm. Compared to the glass, the near-infrared emission in the Cr³⁺-Yb³⁺ codoped glass ceramics is significantly enhanced when the excitation wavelength lies in the range λ~400–800?nm of a solar simulator. Results indicate that the Cr³⁺-Yb³⁺ codoped KZnF₃ glass ceramic provides a promising material for spectral conversion from visible sunlight to near-infrared emission and a novel gain material for solar pumped fiber laser.     

The effect of Nd3+ concentration on fabrication,microstructure, and luminescent properties of anisotropic S-FAP ceramics

Nd³⁺ doped strontium fluorophosphate (S-FAP), with chemical formula Sr₅(PO₄)₃F, nanopowders were prepared using the co-precipitation method. The prepared powders had no impurity phase with a grain size of about 30 nm and the doping limit of Nd³⁺ ions in strontium fluorophosphate is about 9 at.%. The morphology and particle size were determined by the doping concentration of Nd³⁺. Anisotropic Nd: S-FAP transparent ceramics with different Nd³⁺ doping concentrations were fabricated successfully by the simple hot-pressing method. The grain size of prepared S-FAP transparent ceramics decreased first and then increased with the increase of Nd³⁺ concentration. The 2 at.% Nd: S-FAP ceramic presented the highest optical transmittance at all wavelengths range. The characteristic transitions from the ground state to the excited states of Nd³⁺ ions were observed from the absorption spectra, and the absorption cross-section was calculated at 3.71 × 10^–20 cm². The influence of Nd³⁺ ion concentration on luminescence intensity and fluorescence lifetime was studied under 796 nm excitation. The strong emission of ⁴F_3/2→⁴I_9/2 transition in Nd: S-FAP was calculated by Judd–Ofelt (J-O) theory.     

Self-crystallized Ba2LaF7:Nd3+/Eu3+ glass ceramics for optical thermometry

Eu³⁺/Nd³⁺-codoped Ba₂LaF₇ transparent bulk glass ceramics were successfully fabricated by glass self-crystallization. The structure and morphology of the sample were investigated by X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction. The fluorescence intensity ratios of Nd³⁺ emission at 800 nm to the Eu³⁺ emission at 699 nm (⁵D₀ → ⁷F₄) were measured under 578.3 nm laser excitation in a wide temperature range from 290 to 740 K. A relatively good temperature sensing performance was obtained with a maximum relative sensitivity of 1.02% K⁻¹ at 420 K. Both the emission peaks for temperature sensing were located in the optical window of biological tissue, which is favorable for biomedical applications. The results indicate that Ba₂LaF₇:Nd³⁺/Eu³⁺ glass ceramics have a potential application as temperature probes.     

Improved broadband near-infrared luminescence in Nd3+/Tm3+ co-doping tellurite glass with Ag NPs

The near-infrared (NIR) luminescence in S+E+O bands of tellurite glasses doped with Nd³⁺/Tm³⁺ and Ag nanoparticles (NPs) was investigated. The tellurite glasses were prepared by melt-quenching and heat-treated techniques. Under the excitation of 808 nm laser, Nd³⁺/Tm³⁺ doped tellurite glasses produced three NIR luminescence bands of 1.33, 1.47 and 1.85 μm, originating from Nd³⁺:⁴F_3/2→⁴I_13/2, Tm³⁺:³H₄→³F₄ and Tm³⁺:³F₄→³H₆ transitions respectively. Interestingly, a broadband luminescence spectrum ranging from 1280 to 1550 nm with the FWHM (full width at half maximum) about 201 nm was obtained due to the overlapping of the first two NIR bands. Further, the peak intensity of this broadband luminescence was increased by 75% after the introduction of Ag NPs with diameter in 10–20 nm. The analysis of fluorescence decay shows that compared with the enhanced local electric field, the energy transfer from Ag species to Nd³⁺ and Tm³⁺ ions plays a major role in luminescence enhancement. The findings in this work indicate that tellurite glass co-doped with Nd³⁺/Tm³⁺ and Ag NPs is a potential gain material applied in the S+E+O-band photonic devices.     

Multicolor upconversion emission and highly optical temperature sensing based on lanthanide-doped double perovskite Sr2LaNbO6 phosphors

Here we adopt trivalent lanthanide (Ln³⁺ = Er³⁺, Er³⁺/Ho³⁺, and Yb³⁺/Tm³⁺) doped Sr₂LaNbO₆ (SLNO) as novel upconversion luminescence (UCL) materials for achieving UCL and optical temperature sensing under 980 nm excitation. Specifically, Er³⁺ single doped Sr₂LaNbO₆ phosphors present bright high-purity green emission under the 980 nm excitation. While co-doping with the Ho³⁺ ions, the component of red emission from Er³⁺ ions increases significantly and sample show a remarkable enhancement of luminescent intensity relative to SLNO:Er³⁺ sample. The above-mentioned phosphors and Yb³⁺/Tm³⁺ co-doped phosphor (blue emission) successfully achieve high-purity trichromatic UCL and mixed white light output in the same host. Furthermore, the temperature sensing performance of the SLNO:Er³⁺/Ho³⁺ phosphor based on the fluorescence intensity ratio (FIR) is systematically studied for the first time. The temperature sensing based on the non-thermal coupling levels (NTCLs) exhibit higher sensitivity than that based on the thermal coupling levels (TCLs). The maximum absolute and relative sensitivity for ⁴F_9/2/⁴I_9/2 NTCLs reach 0.16803 K^?1 at 427 K and 0.01591 K^?1 at 641 K, respectively. Interestingly, NIR emission of ⁴I_9/2 → ⁴I_15/2 transition presents a thermal enhancement, while visible emissions show thermal quenching. These results indicate that the Ln³⁺ doped Sr₂LaNbO₆ UCL phosphors have potential applications in the fields of non-contact temperature sensors, full-color displays, and anti-counterfeiting.