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.     

Photoluminescence, γ-irradiation and X-ray induced luminescence studies of Sm3+-doped oxyfluorosilicate glasses and glass-ceramics

Sm³⁺-doped oxyfluorosilicate glasses were fabricated through traditional melt quenching technique. After the heat treatment of the prepared glass, transparent SrF₂ nanocrystalline glass-ceramics (GC) were obtained. The amorphous nature of the prepared glasses and crystalline phase (SrF₂) of the GC were confirmed by XRD analysis. Abbe number was calculated for all the prepared glasses by measuring refractive index at different wavelengths. In the framework of Judd-Ofelt (JO) theory, the JO intensity parameters were obtained from the absorption spectra of 1.0 mol% Sm₂O₃-doped glass. The photoluminescence spectrum was recorded with 401 nm excitation. From the analysis of optical spectra and JO parameters, the radiative properties like radiative transition probabilities, branching ratios and radiative lifetimes for the fluorescent levels of Sm³⁺ ions were determined. The effect of γ-irradiation on luminescence properties and X-ray induced luminescence properties were also studied. The emission intensity was increased for GC where as it decreases with increase of γ-irradiation dosages. There are no noticeable changes in the position as well as intensity in photoluminescence and X-ray induced luminescence spectra for GC sample but after the γ-irradiation, the emission intensity was decreased moderately. The luminescence decay profiles for ⁴G_5/2 level were recorded and it is changed from exponential to non-exponential nature for higher Sm³⁺ ion concentrations. The decay profiles which exhibit non-exponential nature are well fitted to the Inokuti-Hirayama model and determined the energy transfer parameters. By using the integrating sphere, the quantum yield values were obtained for all the prepared glasses. The detailed study of the present glasses reveals that these glasses could be useful for radiation shielding and scintillation applications.     

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.     

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.     

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.     

Sensitization of Eu3+ luminescence with titanium(IV) oxide in the composition of nanoparticles in porous glasses

A series of modified porous glasses with a fixed europium content Q(Eu³⁺) = 30 μmol/g and a variable titanium oxide content Q(TiO₂) = 15–375 μmol/g are synthesized. The luminescence properties of the prepared glasses are investigated as a function of the component ratio in the composition of oxide nanoparticles. The specific features of the luminescence quenching in a wet medium are analyzed. It is shown that titanium(IV) oxide substantially sensitizes the photoluminescence of Eu³⁺ ions and shields them against the water adsorption.     

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.     

Effect of neodymium ions on upconversion fluorescence studies of oxyfluorosilicate glasses for optoelectronic devices

Effect of Nd₂O₃ concentrations on optical properties and upconversion studies were investigated for oxyfluorosilicate glasses with composition of SiO₂-Al₂O₃-Na₂CO₃-SrF₂-CaF₂. The Judd-Ofelt (JO) intensity parameters, Ω_λ (λ = 2, 4 and 6) as well as radiative properties for the ⁴F_3/2 level of Nd³⁺ ion have been evaluated from the absorption spectra of 1.0 mol% Nd₂O₃-doped glass. For all the glass samples, the strong NIR emissions were observed at 891, 1058 and 1330 nm and have been attributed to ⁴F_3/2 → ⁴I_{9/2, 11/2, 13/2} transitions respectively. The stimulated emission cross-section for the ⁴F_3/2 → ⁴I_11/2 transition is evaluated and found to be 4.24 × 10^–20 cm². From the decay curves, experimental lifetimes (τ_exp) of the ⁴F_3/2 level have been determined and are found to be 363, 340, 205, 134, 122 and 54 μs for 0.1, 0.5, 1.0, 1.5, 2.0 and 3.0 mol% Nd³⁺ ions doped glasses, respectively. By exciting the prepared glass samples at 808 nm, the upconversion of infrared light into blue, green, yellow and red emission have also observed. These results indicate that the present glasses could be useful for opto-electric devices and solid state laser applications.     

Effect of BaF2 Content on Luminescence of Rare‐Earth Ions in Borate and Germanate Glasses

Rare‐earth‐doped oxyfluoride germanate and borate glasses were synthesized and next studied using spectroscopic methods. Influence of fluoride modifier on luminescence properties of rare earths in different glass hosts was examined. The excitation and emission spectra of Pr³⁺ and Er³⁺ ions in the studied glasses were registered. The emission spectra of Pr³⁺ ions in germanate and borate glasses are quite different and depend strongly on the glass host. In samples doped with Er³⁺ ions emission bands located around 1530 nm corresponding to the main ⁴I_13/2→⁴I_15/2 laser transition were registered, independently of the glass host. Quite long‐lived near‐infrared luminescence of Er³⁺ ions was observed for germanate glasses with low BaF₂ content, while in borate glass systems influence of barium fluoride on luminescence lifetimes is not so evident. The Judd–Ofelt calculations were used in order to determine quantum efficiencies of excited states of rare‐earth ions in germanate and borate glasses.     

A single-phase white-emitting La10(SiO4)6O3：Eu2+/Eu3+ phosphor for near-UV LED-based application

A novel single-phase white-emitting phosphor La₁₀(SiO₄)₆O₃ (LSO): xEu has been synthesized by high-temperature solid-state reaction. Its crystal structure, luminescence properties, fluorescence decay time and oxygen vacancies have been characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. XRD result shows a typical oxyapatite structure with the space group of P6₃/m. Characteristic excitation and emission peaks of Eu²⁺ and Eu³⁺ were observed from PL studies. The optimum doping concentration of Eu was found to be 7.5 mol% (x = 0.075). In this work, the lifetimes of Eu³⁺ and Eu²⁺ were considerably longer than those from some references. Under the excitation of different near ultraviolet (n-UV) longer wavelengths (λex = 360, 370, and 380 nm), the white light emission can be realized with the CIE chromaticity coordinates (0.3907, 0.3595), (0.3472, 0.3282), and (0.3504, 0.3062) for the phosphor LSO: 0.075Eu. The chromaticity coordinates of the phosphor were all located in the white region. Therefore, it is suggested that the explored LSO: 0.075Eu phosphor can be a good candidate for white light-emitting diodes (W-LEDs) application.     

Effects of europium content on structures and luminescence properties of tunable light-emitting silicon oxynitride phosphors

A series of europium (Eu)-activated silicon oxynitride samples with various atomic ratios x of Eu/Si from 0.001 to 0.057 was prepared by employing the polymer-derived method with polycarbosilane and Eu acetylacetonate as starting materials. Chemical compositions, phase structures, morphologies, and luminescence properties of the samples were investigated. It was found that all samples contained a dominated β-Si₃N₄-like phase, and had emission spectra with two peaks. The emission colors of the samples under near-UV excitation were tunable from blue to white, and then to yellow as x in the samples increased from 0.009 to 0.030, and then to 0.057. The white emitting sample with x = 0.030 was in the β-Si₃N₄-like single phase with its particles being single-crystallized in two space groups P6₃ and P6₃/m. Eu²⁺ ions located at interstitial sites of lattices and were coordinated by nine N/O atoms with different average bond lengths for the two space groups. A discussion was given to attribute the difference in the lattice environments for Eu²⁺ ions in two space groups P6₃ and P6₃/m to the appearance of two emission peaks at the lower (597 nm) and higher (454 nm) energy levels for the sample with x = 0.030.     

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.     

Structure and luminescence of Eu doped glass ceramics embedding ZnO quantum dots

Eu³⁺ doped glass ceramics embedding ZnO quantum dots (QDs) were successfully prepared by a sol–gel method. High-resolution transmission electron microscopy (HRTEM) observations revealed that ZnO QDs with size of 3–6 nm precipitated homogeneously among the SiO₂ glassy matrix after thermal treatment of the precursor sample. Such glass ceramics show a high transparency in the visible-infrared range due to the much smaller size of the ZnO QDs than the wavelength of the visible light. The emission and excitation spectra of the samples with various ZnO contents were studied. Based on Judd–Ofelt theory, the intensity parameter Ω₂ was evaluated to investigate the change of the environment around Eu³⁺ in samples with and without QDs.     

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.     

Enhanced luminescence in Tb3+-doped germanate glass ceramic scintillators containing CaF2 nanocrystals

Tb³⁺-doped germanate glass ceramics containing CaF₂ nanocrystals were prepared by melt quenching method with subsequent heat treatment. Their microstructures were investigated by XRD and TEM techniques. Their optical properties were studied by the transmittance, the photoluminescence, and the X-ray excited luminescence (XEL). The luminescence intensity in the glass ceramics under 377 nm light and X-ray excitations is significantly enhanced. The maximum integrated XEL intensity of the glass ceramics is about 50% of that of the commercial Bi₄Ge₃O₁₂ (BGO) scintillating crystal. The results indicate that Tb³⁺-doped germanate glass ceramic could be a promising scintillating material used in X-ray detection for slow event.     

Enhanced photoluminescence quantum yield of Ce3+-doped aluminum–silicate glasses for scintillation application

Ce³⁺-doped 20Gd₂O₃–20Al₂O₃–60SiO₂ (GAS:xCe³⁺) glasses (x = 0.3, 0.7, 1.1, 1.5, 1.9 mol%) with Si₃N₄ as a reducing agent were prepared. The density of the glasses is around 4.2 g/cm³. With the increase in the Ce³⁺ concentration, both the photoluminescence (PL) and PL excitation peaks of GAS:xCe³⁺ glasses show a redshift because the 4f–5d energy levels of Ce³⁺ ions are narrowed. PL quantum yield and PL decay time of GAS:xCe³⁺ glasses are 28.32–50.59% and 43–64 ns, respectively. In addition, they both first increases and then decreases with the Ce³⁺ concentration increasing, reached the maximum when x = 1.1 mol%. The integrated X-ray excited luminescence (XEL) intensity of the GAS:1.1Ce³⁺ glass is 23.86% of that of Bi₄Ge₃O₁₂ (BGO) crystal, and the light yield reaches 1200 ph/MeV with an energy resolution of 22.98% at 662 keV when exposed to γ-rays. The PL and XEL thermal activation energies of GAS:xCe³⁺ glasses are independent of Ce³⁺ ions concentration. Scintillating decay time of the glasses exhibits two components consisting of nanosecond and microsecond levels, and the scintillating decay time gradually decreases with the Ce³⁺ concentration increasing. The difference between PL and scintillating decay time is discussed regarding the different luminescent mechanisms.     

A benign approach for novel synthesis of Eu3+ doped MgNb2O6: Its photoluminescence and photocatalytic studies

The Present work involves the production of Eu³⁺ (1–11 mol %) doped MgNb₂O₆ nanophosphors (NPs) by combustion technique using ODH as a fuel for the first time and well characterized. The average crystallite and the energy gap of the samples were found to be in the range of 20–45 nm and 4.65–5.66 eV respectively, TEM results reflects the same crystallite size values. The effect of doping was confirmed by the characteristic emission peaks recorded at ~535, 590, 614, 642 and 698 nm may be attributed to the 4f–4f intra shell transitions (⁵D₀→⁷F_j=0,1,2,3,4) of Eu³⁺ cations when bombarded at 395 nm energy. Judd–Ofelt parameters (Ω₂, Ω₄), transition probabilities (A_T), quantum efficiency (η), luminescence lifetime (τ_rad) are discussed in detail. From the emission spectra, CIE (Commission International de I’ Eclairage) chromaticity co-ordinates and Correlated color temperature (CCT) were estimated. Langmuir-Hinshelwood model was used to study the photocatalytic degradation of AR-88 dye. The above results confirmed that the present phosphor can be potentially used for display and photocatalytic applications.     

Polychromatic tunable luminescence of Eu3+ doped CsPbBr3 quantum dot glass ceramic induced by mechanical crystallization

Nowadays, inorganic perovskite quantum dots (QDs) glass has become a hot topic in the field of new optical materials. In this work, the Eu³⁺ doped CsPbBr₃ QDs phosphate glass has been successfully prepared. Different from the traditional heat treatment method, the CsPbBr₃ QDs were prepared by mechanical crystallization. When the QDs glass was ground at different times, due to the synergistic effect of red emission (Eu³⁺) and green emission (CsPbBr₃ QDs), the prepared QDs glass can produce the red-yellow-green polychromatic luminescence phenomenon. Benefit from the dual-emission centers of CsPbBr₃ QDs and Eu³⁺ which do not interfere with each other, the relative sensitivity of the temperature sensing is up to 2.11% K^-1, proving that the prepared Eu³⁺ doped QDs glass has practical application in the field of temperature sensing. The glass material obtained in this way not only has tunability and favorable sensitivity but also provides an effective way for the preparation of QDs.     

Processing and luminescence of Eu/Dy-doped Sr2MgSi2O7 glass-ceramics

Glass-ceramics based on the Eu/Dy-doped Sr₂MgSi₂O₇ phosphor have been obtained from sintering and crystallization of glass powders. Electric and gas furnaces were employed for glass melting. The doped parent glasses show red emission under excitation of UV light whereas the corresponding glass-ceramics show blue emission.The microstructure of the glass-ceramics and the crystals responsible for the blue emission were observed by scanning electron microscopy-cathodoluminescence. The composition of the crystallised phases and the distribution and incorporation of rare-earth (RE) ions into the crystals and remaining glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis, respectively.Photoluminescence emission spectra showed a main peak at 484 nm assigned to the typical Eu²⁺ transitions under excitation at 390 nm in the glass-ceramics. The presence of Dy³⁺ improved persistence in the samples melted in the gas furnace. The glass-ceramics are sensitive to temperature, which modifies both the persistence time and red-blue luminescence.     

Emission analysis of CdO–Bi2O3–B2O3 glasses doped with Eu and Tb

This article reports on the emission properties of cadmium bismuth borate (CdBiB) glasses as a function of doping concentrations of Eu³⁺ and Tb³⁺ ions. The functional groups present in the glasses have been identified by analyzing FT-IR spectra. The emission spectra of Eu³⁺ and Tb³⁺:CdBiB glasses have shown reddish green emissions at 616 nm (⁵D₀→⁷F₂) under the excitation at 465 nm and at 547 nm (⁵D₄→⁷F₅) under the excitation at 485 nm, respectively. The Judd–Ofelt (J–O) theory was applied to evaluate the J–O intensity parameters from the absorption and the emission spectra; by using the J–O intensity (Ω_λ) parameters, spontaneous emission transition probability (A), total radiative transition rate (A_T), radiative lifetime (τ_R) and branching ratios (β) of the various emission transitions have been computed for both Eu³⁺ and Tb³⁺:CdBiB glasses. The quenching behavior in the emission intensity with increased concentration of Eu³⁺ and Tb³⁺ was observed, which could be useful for optimizing the compositions toward practical applications.