Search Results (15)

A transparent fluoroborosilicate glass ceramic was designed for the controllable precipitation of fluoride nanocrystals and to greatly enhance the photoluminescence of active ions. Through the introduction of B₂O₃ into fluorosilicate glass, the melting temperature was decreased from 1400 to 1050 °C, and the abnormal crystallization in the fabrication process of fluorosilicate glass was avoided. More importantly, the controlled crystallizations of KZnF₃ and KYb₃F₁₀ in fluoroborosilicate glass ceramics enhanced the emission of Mn²⁺ and Mn²⁺–Yb³⁺ dimers by 6.7 and 54 times, respectively. Moreover, the upconversion emission color of glass ceramic could be modulated from yellow to white and blue by adjusting the Yb³⁺ concentration. The well-designed glass ceramic is a novel and significant compound to simultaneously provide efficiently coordinated sites for transition metal and rare earth ions. More importantly, the design strategy opens a new way for engineering high-quality oxy-fluoride glass ceramics with properties of excellent stability, controllable nano-crystallization and high-efficiency photoluminescence. Full article

Samples of nanocrystalline PbF₂ glass ceramics were obtained by heat-treating SiO₂–GeO₂–PbO–PbF₂–CdF₂ glasses. The Ho₂O₃ and Tm₂O₃ doping effects on the structural features of PbF₂ nanoparticles were studied using small-angle X-ray scattering and X-ray diffraction methods. The enlargements of the average sizes of nanoparticles and the sizes of local areas of density fluctuations have been found to be correlated with an increase in concentrations of Ho₂O₃ and Tm₂O₃ in initial glasses. A variation in the concentrations of Ho₂O₃ and Tm₂O₃ does not affect the morphology and fractal dimension of the formed PbF₂ nanoparticles. Full article

Oxyfluoride glass-ceramics (OxGCs) with the molar composition 80SiO₂-20(1.5Eu³⁺: NaGdF₄) were prepared with sol-gel following the “pre-crystallised nanoparticles route” with promising optical results. The preparation of 1.5 mol % Eu³⁺-doped NaGdF₄ nanoparticles, named 1.5Eu³⁺: NaGdF₄, was optimised and characterised using XRD, FTIR and HRTEM. The structural characterisation of 80SiO₂-20(1.5Eu³⁺: NaGdF₄) OxGCs prepared from these nanoparticles’ suspension was performed by XRD and FTIR revealing the presence of hexagonal and orthorhombic NaGdF₄ crystalline phases. The optical properties of both nanoparticles’ phases and the related OxGCs were studied by measuring the emission and excitation spectra together with the lifetimes of the ⁵D₀ state. The emission spectra obtained by exciting the Eu³⁺-O²⁻ charge transfer band showed similar features in both cases corresponding the higher emission intensity to the ⁵D₀→⁷F₂ transition that indicates a non-centrosymmetric site for Eu³⁺ ions. Moreover, time-resolved fluorescence line-narrowed emission spectra were performed at a low temperature in OxGCs to obtain information about the site symmetry of Eu³⁺ in this matrix. The results show that this processing method is promising for preparing transparent OxGCs coatings for photonic applications. Full article

The remarkable properties of Eu²⁺-activated phosphors, related to the broad and intense luminescence of Eu²⁺ ions, showed a high potential for a wide range of optical-related applications. Oxy-fluoride glass-ceramic containing Europium (II)-doped CaF₂ nanocrystals embedded in silica matrix were produced in two steps: glass-ceramization in air at 800° with Eu³⁺-doped CaF₂ nanocrystals embedded followed by Eu³⁺ to Eu²⁺ reduction during annealing in reducing atmosphere. The broad, blue luminescence band at 425 nm and with the long, weak tail in the visible range is assigned to the d → f type transition of the Eu²⁺ located inside the CaF₂ nanocrystals in substitutional and perturbed sites, respectively; the photoluminescence quantum yield was about 0.76. The X-ray photoelectron spectroscopy and Electron paramagnetic spectroscopy confirmed the presence of Eu²⁺ inside the CaF₂ nanocrystals. Thermoluminescence curves recorded after X-ray irradiation of un-doped and Eu²⁺-doped glass-ceramics showed a single dominant glow peak at 85 °C related to the recombination between F centers and Eu²⁺ related hole within the CaF₂ nanocrystals. The applicability of the procedure can be tested to obtain an oxy-fluoride glass-ceramic doped with other divalent ions such as Sm²⁺, Yb²⁺, as nanophosphors for radiation detector or photonics-related applications. Full article

LaF₃ is commonly added to oxide glass, in particular to silica, to form oxyfluoride glass. After appropriate thermal treatment at a temperature lower than 800 °C, usually, glass ceramics are obtained. Recently, LaF₃ nanoparticles have been used as precursors to obtain amorphous nanoparticles of undefined composition in optical fiber. However, fiber fabrication necessitates temperature much higher (typically up to 2000 °C) than the one required for bulk glass. In this article, we report on the reactivity of fluoride ions in LaF₃ with SiO₂ and GeO₂ (a common dopant used to dope optical fiber) powders at high temperature. TGA, EDX-SEM, XRD and Raman analyses were performed. Above 1000 °C, LaF₃ starts to react, preferentially with SiO₂, to form SiF₄ gaseous species. The remaining lanthanum ions form La₂Si₂O₇ and La₂Ge₂O₇ phases. These results could contribute to improve material development for the fiber optics community. Full article

The synthesis and characterization of multicolor light-emitting nanomaterials based on rare earths (RE³⁺) are of great importance due to their possible use in optoelectronic devices, such as LEDs or displays. In the present work, oxyfluoride glass-ceramics containing BaF₂ nanocrystals co-doped with Tb³⁺, Eu³⁺ ions were fabricated from amorphous xerogels at 350 °C. The analysis of the thermal behavior of fabricated xerogels was performed using TG/DSC measurements (thermogravimetry (TG), differential scanning calorimetry (DSC)). The crystallization of BaF₂ phase at the nanoscale was confirmed by X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM), and the changes in silicate sol–gel host were determined by attenuated total reflectance infrared (ATR-IR) spectroscopy. The luminescent characterization of prepared sol–gel materials was carried out by excitation and emission spectra along with decay analysis from the ⁵D₄ level of Tb³⁺. As a result, the visible light according to the electronic transitions of Tb³⁺ (⁵D₄ → ⁷F_J (J = 6–3)) and Eu³⁺ (⁵D₀ → ⁷F_J (J = 0–4)) was recorded. It was also observed that co-doping with Eu³⁺ caused the shortening in decay times of the ⁵D₄ state from 1.11 ms to 0.88 ms (for xerogels) and from 6.56 ms to 4.06 ms (for glass-ceramics). Thus, based on lifetime values, the Tb³⁺/Eu³⁺ energy transfer (ET) efficiencies were estimated to be almost 21% for xerogels and 38% for nano-glass-ceramics. Therefore, such materials could be successfully predisposed for laser technologies, spectral converters, and three-dimensional displays. Full article

Transparent oxyfluoride glass-ceramics (GCs) with embedded β-Na₁.₅Y₁.₅F₆ crystals doped with Er³⁺ ions were fabricated by a melt-quenching method with subsequent heat-treatment. The structural characterizations and spectroscopic techniques were performed to verify the precipitation of β-Na₁.₅Y₁.₅F₆ crystals and partition of the Er³⁺ dopant into the crystals. Bright green up-conversion (UC) emission was achieved in Er³⁺-doped glass-ceramic (Er-GC). Furthermore, the temperature-dependent visible UC behavior based on thermally coupled energy levels (TCLs) and non-thermally coupled energy levels (NTCLs) was also examined in the temperature range 298 k to 823 K with maximum relative sensitivity (S_r) of 1.1% K⁻¹ at 298 K for TCLs in Er-G and Er-GC samples. Full article

Rare-earth doped oxyfluoride glass ceramics represent a new generation of tailorable optical materials with high potential for optical-related applications such as optical amplifiers, optical waveguides, and white LEDs. Their key features are related to the high transparency and remarkable luminescence properties, while keeping the thermal and chemical advantages of oxide glasses. Sol-gel chemistry offers a flexible synthesis approach with several advantages, such as lower processing temperature, the ability to control the purity and homogeneity of the final materials on a molecular level, and the large compositional flexibility. The review will be focused on optical properties of sol-gel derived nano-glass ceramics related to the RE-doped luminescent nanocrystals (fluorides, chlorides, oxychlorides, etc.) such as photoluminescence, up-conversion luminescence, thermoluminescence and how these properties are influenced by their specific processing, mostly focusing on the findings from our group and similar ones in the literature, along with a discussion of perspectives, potential challenges, and future development directions. Full article

In this study, transparent oxyfluoride glass-ceramics (GCs) with NaLaF₄ nanocrystals (NCs) were prepared by the sol–gel method for the first time. Three different molar ratios of La(CH₃COO)₃/Na(CH₃COO) were used to obtain the GCs, which were sintered at 450, 550 and 650 °C for 1 min. X-ray diffraction (XRD) was employed to follow the evolution of the xerogel during the heat treatments and to study crystal growth for the three temperatures. In all cases, the LaF₃ crystalline phase was present, but crystallization of NaLaF₄ was only promoted at 650 °C. Thermogravimetric and thermodifferential analysis (TGA-DTA) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the crystallization process. High-resolution transmission electron microscopy (HRTEM) was employed to confirm NaLaF₄ crystallization and determine the size distribution. The incorporation of Nd³⁺ ion into NaLaF₄ and LaF₃ nanocrystals was confirmed by site-selective emission and excitation spectra. The Nd³⁺ emission intensities in both phases depend not only on the NaLaF₄/LaF₃ ratio but also on their emission efficiencies. Full article

In this work, we performed a systematic analysis of the impact of selected chemical reagents used in sol-gel synthesis (i.e., N,N-dimethylformamide) and different catalyst agents (i.e., CH₃COOH, HNO₃) on the formation and luminescence of Eu³⁺-doped SiO₂–LaF₃ nano-glass–ceramics. Due to the characteristic nature of intra-configurational electronic transitions of Eu³⁺ ions within the 4f⁶ manifold (⁵D₀ → ⁷F_J, J = 0–4), they are frequently used as a spectral probe. Thus, the changes in the photoluminescence profile of Eu³⁺ ions could identify the general tendency of rare earth materials to segregate inside low-phonon energy fluoride nanocrystals, which allows us to assess their application potential in optoelectronics. Fabricated sol-gel materials, from sols to gels and xerogels to nano-glass–ceramics, were examined using several experimental techniques: X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), and luminescence measurements. It was found that the distribution of Eu³⁺ ions between the amorphous silicate sol-gel host and LaF₃ nanocrystals is strictly dependent on the initial composition of the obtained sols, and the lack of N,N-dimethylformamide significantly promotes the segregation of Eu³⁺ ions inside LaF₃ nanocrystals. As a result, we detected long-lived luminescence from the ⁵D₀ excited state equal to 6.21 ms, which predisposes the obtained glass–ceramic material for use as an optical element in reddish-orange emitting devices. Full article

Transparent fluorotellurite glasses were prepared by melt-quenching in the ternary system TeO₂-Nb₂O₅-PbF₂. The synthesis conditions were adjusted to minimize fluorine loss monitored as HF release. It was found that 10 mol% of Nb₂O₅ is the optimum content for PbF₂ incorporation up to 35 mol% in the tellurite matrix without loss of glass forming ability. Such glass compositions exhibit a wide optical window from 380 nm to about 6 μm. Crystallization properties were carefully investigated by thermal analysis and compositions with higher PbF₂ contents exhibit preferential precipitation of lead oxyfluoride Pb₂OF₂ at lower temperatures. The lead oxyfluoride crystallization mechanism is also governed by a volume nucleation, barely reported in tellurite glasses. Eu³⁺ doping of these glass compositions also promotes a more efficient nucleation step under suitable heat-treatments, resulting in transparent Eu³⁺-doped glass-ceramics whereas undoped glass-ceramics are translucent. Finally, Eu³⁺ spectroscopy pointed out a progressive, more symmetric surrounding around the rare earth ions with increasing PbF₂ contents as well as higher quantum efficiencies. These new fluorotellurite glass compositions are promising as luminescent hosts working in the middle infrared. Full article

Transparent oxyfluoride glass–ceramics containing NaGdF₄ nanocrystals were prepared by melt-quenching and doped with Er³⁺ (0.5 mol%) and different amounts of Yb³⁺ (0–2 mol%). The selected dopant concentration the crystallization thermal treatments were chosen to obtain the most efficient visible up-conversion emissions, together with near infrared emissions. The crystal size increased with dopant content and treatment time. NaGdF₄ NCs with a size ranging 9–30 nm were obtained after heat treatments at T_g + 20–80 °C as confirmed by X-ray diffraction and high-resolution transmission electron microscopy. Energy dispersive X-ray analysis shows the incorporation of rare earth ions into the NaGdF₄ nanocrystals. Near-infrared emission spectra, together with the up-conversion emissions were measured. The optical characterization of the glass–ceramics clearly shows that Er³⁺ and Yb³⁺ ions are incorporated in the crystalline phase. Moreover, visible up-conversion emissions could be tuned by controlling the nanocrystals size through appropriated heat treatment, making possible a correlation between structural and optical properties. Full article

The ErF₃-doped oxyfluoride phospho-tellurite glasses in the (40-x) TeO₂-10P₂O₅-45 (BaF₂-ZnF₂) -5Na₂O-xErF₃ system (where x = 0.25, 0.50, 0.75, 1.00, and 1.25 mol%) have been prepared by the conventional melt-quenching method. The effect of erbium trifluoride addition on thermal, structure, and spectroscopic properties of oxyfluoride phospho-tellurite precursor glass was studied by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR), and Raman spectroscopy as well as emission measurements, respectively. The DSC curves were used to investigate characteristic temperatures and thermal stability of the precursor glass doped with varying content of ErF₃. FTIR and Raman spectra were introduced to characterize the evolution of structure and phonon energy of the glasses. It was found that the addition of ErF₃ up to 1.25 mol% into the chemical composition of phospho-tellurite precursor glass enhanced 2.7 µm emission and upconversion. By controlled heat-treatment process of the host glass doped with the highest content of erbium trifluoride (1.25 mol%), transparent erbium-doped phospho-tellurite glass-ceramic (GC) was obtained. X-ray diffraction analysis confirmed the presence of BaF₂ nanocrystals with the average 16 nm diameter in a glass matrix. Moreover, MIR, NIR, and UC emissions of the glass-ceramic were discussed in detail and compared to the spectroscopic properties of the glass doped with 1.25 mol% of ErF₃ (the base glass). Full article

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO₂-20LaF₃ doped with Er³⁺ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 µm were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF₃ crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF₃ nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er³⁺ ions are preferentially embedded in the low phonon-energy LaF₃ nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF₃ nanocrystals. The effective concentration of rare-earth ions in the LaF₃ nanocrystals is also estimated by X-ray absorption spectroscopy. Full article

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF₄ glass-ceramics. Moreover, a new SiO₂ precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications. Full article