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.     

Eu3+‐Activated Borogermanate Scintillating Glass with a High Gd2O3 Content

Eu³⁺‐activated borogermanate scintillating glasses with compositions of 25B₂O₃–40GeO₂–25Gd₂O₃–(10?x)La₂O₃–xEu₂O₃ were prepared by melt‐quenching method. Their optical properties were studied by transmittance, photoluminescence, Fourier transform infrared (FTIR), Raman and X‐ray excited luminescence (XEL) spectra in detail. The results suggest that the role of Gd₂O₃ is of significance for designing dense glass. Furthermore, energy‐transfer efficiency from Gd³⁺ to Eu³⁺ ions can be near 100% when the content of Eu₂O₃ exceeds x = 4, the corresponding critical distance for Gd³⁺–Eu³⁺ ion pairs is estimated to be 4.57 Å. The strongest emission intensities of Eu³⁺ ions under both 276 and 394 nm excitation are simultaneously at the content of 8 mol% Eu₂O₃. The degree of Eu–O covalency and the local environment of Eu³⁺ ions are evaluated by the value of Ω_t parameters from Judd–Ofelt analysis. The calculated results imply that the covalency of Eu–O bond increases with the increasing concentration of Eu³⁺ ions in the investigated borogermanate glass. As a potential scintillating application, the strongest XEL intensity under X‐ray excitation is found to be in the case of 6 mol% Eu₂O₃, which is slightly different from the photoluminescence results. The possible reason may be attributed to the discrepancy of the excitation mechanism between the ultraviolet and X‐ray energy.     

Eu3+-doped transparent potassium lanthanum silicate (KLaSiO4) glass-ceramic nanocomposites: Synthesis,properties and application

The preparation of Eu³⁺-doped novel K₂O-La₂O₃-Al₂O₃-SiO₂ (KLAS)-based glass and transparent KLS (KLaSiO₄) glass–ceramic (GC) nanocomposites is reported. Nanostructures of the transparent GCs were analyzed by FE-SEM, H(R)-TEM and SAED techniques. The average size of the crystallites is calculated using XRD data and found to be in the range 13–19?nm which is matched well with the average particle size observed from TEM images in the range 5–18?nm. Photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀?→?⁷F_j (j?=?0 and 1–4) under the excitation at 394?nm. The emission spectra reveals up to 3-fold enhancement of luminescence performance of the KLS GC nanocomposites compared to as-prepared glass. This enhancement is caused due to entering of Eu³⁺ ions into the KLS crystal sites by replacing the La³⁺ ions. Such luminescence properties of KLS glass-ceramic nanocomposites could be a promising candidate as laser host for many laser devices.     

Synthesis and Characterization of Eu3+‐Doped Transparent Glass–ceramics Containing Nanocrystalline SrIINbIVO3

The glass–ceramics containing a rarely achievable nanocrystalline Sr^IINb^IVO₃ phase in the 53.75SiO₂–18.25K₂O–9Bi₂O₃–9SrO–9Nb₂O₅–0.5CeO₂–0.5Eu₂O₃ (mol%) glass system were prepared by the melt‐quench technique followed by a two‐stage controlled heat treatment. The unusual oxidation state of Nb in Sr^IINb^IVO₃ crystal is 4+ and upon heat treatment of the samples at lower temperature of 500°C for several hours, the glass composition and chemical environment around Nb ions played a key role for the formation of Sr^IINb^IVO₃ in the glass–ceramics. The microstructure of the glass–ceramics was studied using TEM and FESEM. The TEM images advocate 10–40 nm crystallite size of Sr^IINb^IVO₃. FTIR study confirms that all the samples consist of SiO₄, BiO₃, BiO₆, and NbO₆ structural units. The refractive index at different wavelengths was found to vary in the range 1.7105–1.7905 and increase with increase in heat‐treatment time. The luminescence spectra of Eu³⁺‐doped glass and glass–ceramics were recorded at 465 nm excitation wavelength and the luminescence intensity is found to be increased with heat‐treatment time due to increase in crystallinity. The high intensity ratio of ⁵D₀→⁷F₂ to ⁵D₀→⁷F₁ indicates that the Eu³⁺‐doped nanocrystalline Sr^IINb^IVO₃ glass–ceramics are promising candidate materials as red‐light source.     

Eu2+‐Doped Yellow‐Emitting CsBaB3O6 Glass‐Ceramic Prepared by Melt Quenching and Re‐Crystallization Method

Eu³⁺‐doped cesium barium borate glass with the composition of Cs₂O·2BaO·3B₂O₃ was prepared by the conventional melt quenching method. The glass‐ceramic sample was obtained from the re‐crystallization of the as‐made glass to change the amorphous glass into a crystalline host. This reduces the Eu³⁺ in glass to Eu²⁺ ions resulting in a yellow‐emitting phosphor of Eu²⁺‐activated CsBaB₃O₆. The samples were investigated by the XRD patterns and SEM micrograph, the optical absorption, the photoluminescence spectra, and decay curves. The as‐made glass has only Eu³⁺ centers. Under the excitation of blue or near‐UV light, Eu²⁺‐doped CsBaB₃O₆ presents yellow‐emitting color from the allowed inter‐configurational 4f–5d transition in the Eu²⁺ ions. The maximum absolute luminescence quantum efficiencies of Eu²⁺‐doped CsBaB₃O₆ phosphor was measured to be 47% excited at 430 nm light at 300 K. By taking into account the efficient excitation in blue wavelength region, this new phosphor could be a potential yellow‐emitting phosphor for an application in white light‐emitting diodes fabricated with blue chips.     

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.     

Effect of the Eu3+ Addition on Photoluminescence and Microstructure of ZnO–CdO–TeO2 Glasses

In this work, the role of europium doping of glasses formulated in the ternary system ZnO–CdO–TeO₂ is described. The Eu‐doped oxide glasses were prepared by the conventional melt‐quenching method and by using three different compositions. Structural studies reveal that there exists a good affinity between Cd and some rare earth (RE) ions to form the crystalline phase. The X‐ray diffraction (XRD) diagrams display that the structure of these glasses is amorphous and with the increase in CdO content and the compatibility of Eu³⁺, there is a tendency to form nanocrystals of CdTe₂O₅. The scanning electron microscopic (SEM) observation of their microstructure confirms the presence of phase separation. Differential thermal analysis (DTA) of these glasses showed small exothermic peaks noted around 450°C for the V2 glass and 480°C for V1 and V3 glasses, which could be attributed to the formation of these crystals. The infrared spectra showed a main absorption band around 800–600 cm^?1 corresponding to the Te–O stretching mode in TeO₄ and TeO₃ groups. By optical absorption (OA), the band gap (E_g) for each glass was determined; these values were 3.27, 3.14, and 3.3 eV for the V1–V3 glasses, respectively. Furthermore, the presence of Eu³⁺ was detected in the 370–470 nm short‐range wavelengths. The photoluminescence (PL) experiments of the glasses showed light emission due to the following transitions: ⁵D₀ → ⁷F₁, ⁵D₀ → ⁷F₂, ⁵D₀ → ⁷F₃, and ⁵D₀ → ⁷F₄.     

Enhanced Light Storage of SrAl2O4 Glass‐Ceramics Controlled by Selective Europium Reduction

A luminescent Eu, Dy: SrAl₂O₄ glass‐ceramics with high transparency in the visible region was successfully synthesized using the frozen sorbet technique with the control of O₂ partial pressure () for the oxidation of Eu²⁺ ions. The glass‐ceramics include Eu²⁺, Eu³⁺, and Dy³⁺ ions, and thus exhibits three characteristic types of emission bands, 4f–5d at around 520 nm (Eu²⁺ ions), 4f–4f at 610 nm (Eu³⁺ ions), and 480 nm (Dy³⁺ ions). The Eu, Dy: SrAl₂O₄ glass‐ceramics provide remarkable long‐persistent luminescence under dark condition. The glass‐ceramics also exhibits color‐changing luminescence in the visible region based on their remarkable light storage properties. The luminescent Eu, Dy: SrAl₂O₄ glass‐ceramics using the frozen sorbet technique with control of are promising materials for application in novel photonic and light storage materials.     

Synthesis of Eu3+‐doped BaBi2Ta2O9 based glass‐ceramic nanocomposites: Optical and dielectric properties

In this paper we report for the first time synthesis of Eu³⁺‐doped transparent glass‐ceramics (TGC) with BaBi₂Ta₂O₉ (BBT) as the major crystal phase using the glass system SiO₂–K₂O–BaO–Bi₂O₃–Ta₂O₅ by melt quenching technique followed by controlled crystallization through ceramming heat treatment. DSC studies were conducted in order to determine a novel heat‐treatment protocol to attain transparent GCs by controlling crystal growth. The structural properties of the BBT GCs have been investigated using XRD, FE‐SEM, TEM and FTIR reflectance spectroscopy. Optical band gap energies of the glass‐ceramic samples were found to decrease with respect to the precursor glass. An increased intensity of emission along with increase in the average lifetime of Eu³⁺ was observed due to incorporation of Eu³⁺ ions into the low‐phonon energy BBT crystal site. The local field asymmetric ratios of all the samples were observed greater than unity. The dielectric constant (ε_r), dielectric loss, and dissipation factor values of both the base glass and ceramized samples were found to decrease with increase in frequency.     

Persistent luminescence of Eu/Dy-doped Sr2MgSi2O7 glass-ceramics processed by aerodynamic levitation

Glass beads of the Sr₂MgSi₂O₇ stoichiometric composition and a non-stoichiometric composition with higher SiO₂/SrO ratio doped with Eu₂O₃/Dy₂O₃ were prepared through aerodynamic levitation coupled to CO₂ laser heating. The glass beads were subsequently treated at 1100 ºC to produce glass-ceramics with Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ as the main crystalline phase. The doped glasses exhibit red emissions; after crystallisation, the corresponding glass-ceramics emit blue light under UV excitation. The starting glass composition considerably affects the crystallisation process, resulting in Sr₂MgSi₂O₇ glass-ceramics with very different microstructures which, in turn, have a significant influence on the luminescence properties. The photoluminescence emission spectra of the glass-ceramics under UV light show a broadband emission (λ = 400–500 nm) with a main peak assigned to the typical Eu²⁺ transition under excitation at 365 nm. Both the intensity of the emission and the persistence time significatively increase on decreasing temperature. Glass-ceramics from the non-stoichimetric glass composition co-doped with 1Eu₂O₃/0.5Dy₂O₃ (mol%.) provided the longest persistence times.     

Radiation response properties of Eu3+-doped K2O–Ta2O5–Ga2O3 glasses

Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were synthesized, and their radiation response characteristics were studied systematically. According to their photoluminescence spectra, they showed intense emissions with sharp peaks centered at around 580, 594, 613, 656, and 706 nm when irradiated by 380 nm light. The sharp peaks originate from the 4f-4f transitions of Eu³⁺. Moreover, these sharp peaks were also detected when excited by X-ray, and the 1.0% Eu₂O₃-doped gallate glasses showed the largest luminescence intensity under UV light and X-ray. Furthermore, the afterglow levels of the Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were determined to be approximately 300 ppm. These levels are close to the levels of TI-doped CsI single crystals.     

Coloration and Nonlinear Optical Properties of ZnTe Quantum Dots in ZnO–TeO2–P2O5 Glasses

ZnO–TeO₂–P₂O₅ glasses were prepared by melt‐quenching method. The color of the glass samples changed from colorless to pale red and dark red with increasing TeO₂ content. Coloration mechanism and nonlinear optical properties of ZnO–TeO₂–P₂O₅ glasses have been investigated. Raman spectra and transmission electron microscope measurements indicated the precipitation of ZnTe quantum dots in the glasses and ZnTe quantum dots are the origin of coloration. Z‐scan technique was used to examine the nonlinear optical properties of the glasses. The glass sample with 30 mol% TeO₂ exhibits large third‐order nonlinear optical susceptibility of 10^?11 esu.     

Intense red emission via energy transfer from (Ce3+/Eu3+):P2O5+NaF+CaF2+AlF3 glasses for warm light sources

Europium (Eu³⁺)-doped fluorophosphate (PNCA:P₂O₅+NaF + CaF₂+AlF₃) glasses with the addition of cerium (Ce³⁺) ions were fabricated by the melt-quenching technique to know their ability for the bright red (615 nm) luminescence. The emission (PL) and excitation (PLE) spectra, decay curve measurements as well as energy transfer (ET) process of Ce³⁺→ Eu³⁺ were studied in detail. An excitation spectrum related to the ⁷F₀→ ⁵D₂ level of Eu³⁺ is used to estimate the phonon energy (1121 cm^?1) of the title glass host. Under ultraviolet (UV) irradiation of 299 nm, the PL spectra of (Ce³⁺/Eu³⁺):PNCA glasses show intense red emission at 615 nm whereas the lifetime decrease with respect to increase of Eu³⁺ that could support the observed efficient ET from Ce³⁺ to Eu³⁺. The ET:Ce³⁺ →Eu³⁺ via quadrupole-quadrupole process was confirmed by Reisfeld's approximation and Dexter's ET formula. The ET efficiency (η_ET) and critical distance (R_c) were also calculated. Interestingly, the (Ce³⁺/Eu³⁺):PNCA glasses showed intense red light emission with low correlated color temperatures and the corresponding color purity reached as great as 99%, indicating its potentiality as a red component for warm light sources.     

Study of Eu3+–Gd3+ co-doped Ba–Bi–B glasses for red-laser applications: Physical,structural, photoluminescence and time-resolved spectral characteristics

A series of Eu³⁺ and Eu³⁺/Gd³⁺ co-doped barium-bismuth-borate (Ba–Bi–B) glasses were prepared by melt-quench technique. And deliberated the physical, structural, and spectroscopic properties of all glasses and explored the energy transfer process from Gd³⁺ to Eu³⁺ ions. The density of glasses increased with increasing of Gd³⁺ concentration in co-doped glasses. Characteristics of steady-state and time-resolved photoluminescence (PL) of Eu-doped and Eu³⁺-Gd³⁺ co-doped glasses under different excitation wavelengths suggested the prospects of the investigated glass system for display device applications. PL spectrum displays a strong red emission peak centered at 612 nm due to the Eu³⁺: ⁵D₀→ ⁷F₂ transition. Less intense emissions centered at 577 nm (⁷F₀), 590 nm (⁷F₁), 651 nm (⁷F₃) and 700 nm (⁷F₄) are also observed from the radiative transitions of the excited state ⁵D₀ of Eu³⁺ions. The values of radiative parameters such as transition probability, branching ratios, and stimulated emission cross-sections were obtained from Judd–Ofelt theory analysis and indicated the aptness of the Ba–Bi–B glasses for optical devices. A 5-fold enhancement in the PL intensity was observed in 1.0 mol% Eu³⁺ and 3.0 mol% Gd³⁺ co-doped glass under λ_Exci. = 394 nm excitation. The calculated commission Internationale de l'eclairage color coordinates and correlated color temperature values show that the Ba–Bi–B glasses are useful for red-laser and display device applications.     

Effect of the Glass Structure on Emission of Rare‐Earth‐Doped Borate Glasses

A series of glasses composed of xB₂O₃–8Al₂O₃‐(90?x)Na₂O–R₂O₃ (x = 65, 70, 75, 80, 85; R = Dy³⁺, Tb³⁺, Sm³⁺) were prepared through melt‐quenching. Structural evolution was induced by varying the glass composition. Increasing the glass network former B₂O₃ enhanced the luminescence of rare‐earth ions, as observed in the emission spectra. The mechanism of the glass structural evolution was investigated by the NMR spectra analysis. The dispersant effect of the glass structure was believed to promote the better distribution of the rare‐earth ions in the matrix and reduced the concentration quenching between them. The relationship between the glass structure and its optical properties was established.     

Effective sensitization of Eu3+ ions on Eu3+/Nd3+ co-doped multicomponent borosilicate glasses for visible and NIR luminescence applications

Eu³⁺/Nd³⁺ co-doped multicomponent borosilicate glasses (ND1E: 10BaO +10ZnF₂+10K₂O +20SiO₂+(49-x) B₂O₃+1Nd₂O₃+xEu₂O₃) were prepared by conventional melting and rapid quench technique to evaluate the effect of Eu³⁺ ions in the Nd³⁺ doped glasses. Thermal stability, structural and spectroscopic characteristics of the ND1E glasses were investigated by using DSC, XRD, FTIR, Optical absorption, excitation and emission measurements. The Judd – Ofelt (JO) analysis is implemented to the absorption spectrum of the prepared glassy matrix in order to identify their potential applicability in lasing devices. Enhancement of ⁷F₀ → ⁵L₆ band (394 nm) with the increasing concentration of Eu³⁺ ion in the Nd³⁺ excitation spectra (λ_emi = 1060 nm) reveals the possibility of obtaining the characteristic fluorescence spectra of Nd³⁺ ion with the typical excitation wavelengths (Nd³⁺ = 584 nm and Eu³⁺ = 394 nm) of both rare earth ions and it is further verified from the emission spectrum. This interesting luminescence effect of showing excellent visible and NIR emission under 394 nm excitation mainly attributes the energy transfer mechanism between the RE³⁺ ions and the reason underlying this effect is discussed in detail with the help of partial energy level diagram. Energy transfer efficiency between the Eu³⁺ and Nd³⁺ ions were evaluated by using the radiative lifetimes of the prepared glasses. Also, a comparison of radiative properties and lasing characteristics of Eu³⁺/Nd³⁺ co-doped glasses with other Nd³⁺ glasses are reported. The emission intensities were characterized using CIE chromaticity diagram and the observed CIE coordinates shows a shift towards reddish – orange region with the increase in Eu³⁺ concentration. The quantum efficiency of the prepared glasses was determined experimentally. The obtained results suggest that the ND1E glassy system can be considered as a potential candidate for visible and NIR luminescence applications.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Frequency and Temperature‐Independent Electrical Transport Properties of 2BaO–0.5Na2O–2.5Nb2O5–4.5B2O3 Glass‐Ceramics

The temperature (300–973 K) and frequency (100 Hz–10 MHz) response of the dielectric and impedance characteristics of 2BaO‐0.5Na₂O–2.5Nb₂O₅–4.5B₂O₃ glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100 Hz–10 MHz) and temperature (300–600 K). The temperature coefficient of dielectric constant was 8 ± 3 ppm/K in the 300–600 K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal‐glass interface, leading to a high value of effective dielectric constant especially for the samples heat‐treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P_r) increased with the increase in crystallite size.     

Tuning the Color Emission of Sr2P2O7: Tb3+, Eu3+ Phosphors Based on Energy Transfer

A series of color tunable Tb³⁺‐ and Eu³⁺‐activated Sr₂P₂O₇ phosphors were synthesized by a traditional solid‐state reaction method in air atmosphere. The crystal structure, photoluminescence (PL) properties, energy transfer, thermal stability, and luminous efficiency were investigated. A series of characteristic emission of Tb³⁺ and Eu³⁺ were observed in the PL spectra and the variation in the emission intensities of the three emission peaks at around 416 nm (blue), 545 nm (green), and 593 nm (orange‐red) induced the multicolor emission evolution by tuning the Tb³⁺/Eu³⁺ content ratio. The energy‐transfer mechanism from Tb³⁺ to Eu³⁺ ion was determined to be dipole–dipole interaction, and the energy‐transfer efficiency was about 90%. The novel phosphors have excellent thermal stability in the temperature range of 77–473 K and the Commission International De L'Eclairage 1931 chromaticity coordinates of Sr₂P₂O₇: Tb³⁺, Eu³⁺ (λ_ex = 378 nm) move toward the ideal white light coordinates.     

Effects of Tm3+ Additions on the Crystallization of LaF3 Nanocrystals in Oxyfluoride Glasses: Optical Characterization and Up‐Conversion

The influence of the addition of 1 mol% Tm₂O₃ on the nanocrystallization of LaF₃ in a glass of composition 55SiO₂–20Al₂O₃–15Na₂O–10LaF₃ (mol%) has been studied. Tm₂O₃ affects the phase separation in the glass and delays the onset of crystallization with respect to the undoped glass. Additionally, the maximum LaF₃ crystal size is slightly greater than that in the undoped glass–ceramics. The microstructural and compositional changes in the glass matrix have been studied using several techniques, including viscosity, dilatometry, X‐ray and neutron diffraction (XRD, ND), quantitative Rietveld refinement, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and Raman spectroscopy. Photoluminescence measurements indicate that the Tm³⁺ ions are distributed between the glassy matrix and LaF₃ crystals. Eu₂O₃ has been used as structure probe and part of the Eu³⁺ ions are reduced to Eu²⁺ when incorporated in the LaF₃ nano‐crystals. Up‐conversion spectra under IR‐excitation show a higher intensity of the blue emission in the Tm‐doped glass–ceramic compared with that in the glass.