Zinc Borophosphate Glasses Research Articles

Physical, optical and spectral properties of Sm3+ and Eu3+ ions doped zinc boro-phosphate glass

This study focuses on the synthesis of Sm³⁺ and Eu³⁺ rare earth ions doped zinc boro-phosphate glasses and their physical, optical and spectral characterization. Photoluminescence was carried out through both steady-state and time-domain luminescence measurements. The glasses were prepared via the melt quenching technique, and they exhibit impressive mechanical strength and transparency. Judd-Ofelt analysis of the near-infrared absorption spectra revealed parameters Ω₂, Ω₄, and Ω₆, indicating low covalency and reduced site asymmetry for the rare earth ions compared to those in silicate-based glasses. When excited with violet light, the Sm³⁺-doped samples emitted bright orange luminescence, resulting from radiative relaxation from the ⁴G₅/₂ state to lower energy levels. The calculated branching ratios correspond well with the observed emission peak ratios. However, increasing the Sm³⁺ ion concentration resulted in reduced luminescence intensity and shorter fluorescence lifetimes, due to cross-relaxation effects. In the Sm³⁺/Eu³⁺ co-doped glasses, energy transfer from Sm³⁺ to Eu³⁺ ions was detected upon selective excitation of Sm³⁺ ions. This energy transfer efficiency was found to increase with higher concentrations of Eu³⁺ ions.

Optical and luminescent properties of Dy3+/Sm3+ doped and codoped Zinc Borophosphate glasses for W-LED application

In this work, a series of zinc borophosphate glasses (ZnPBAl), doped and codoped with Dy3+ and Sm3+, was studied for potential application in W-LEDs. The samples were prepared by the melt-quenching method and their luminescent and optical properties were investigated. The optical absorption spectra presented all Dy3+ and Sm3+ peaks corresponding to the transitions from the 6H15/2 and 6H5/2 states, respectively, to the excited energy levels. The 350 nm excitation source was chosen, considering photoluminescence excitation (PLE) results, to investigate the energy transfer from Dy3+ to Sm3+ ions. The energy transfer was indicated by photoluminescence (PL) spectra of Dy:Sm-codoped glasses and investigated by the energy transfer efficiency (η) using the lifetime data of both doped and codoped samples. The PL as a function of temperature was also studied. The CIE diagram of Dy-doped glasses showed their color emission close to the white region and the simulation of a combined Blue LED created an illumination route from warm to cold white light.

Synthesis structural optical and mechanical properties of Nb3⁺ doped Zinc Borophosphate glass for radiation shielding application

Abstract The Nb3⁺ doped Zinc Borophosphate glass (30B2O3 +35P2O5+5TiO2+10ZnO+9LiCO3+10 BaCO3+1NbO2) has been synthesized successfully using melt-quenching method. The powder X-ray diffraction (XRD) analysis was used to find the glass nature of Nb3⁺ doped Zinc Borophosphate glass. The functional group of Nb3⁺ doped Zinc Borophosphate glass was recognized using Fourier-transform infrared spectroscopy (FTIR) analyses. Linear optical properties of the Nb3⁺ doped Zinc Borophosphate glass were studied using UV–vis–NIR spectrum in the room temperature. Mechanical behaviour of Nb3⁺ doped Zinc Borophosphate glass was examined through Vicker’s hardness method. The mechanical properties of Nb3⁺ doped Zinc Borophosphate glass was examined with various loads. The emission transitions of Nb3⁺ doped Zinc Borophosphate glass was studied using Photoluminescence analysis. The CIE diagram of the Photoluminescence was examined. Gamma ray shielding parameters such half value layer, mean free path and mass attenuation coefficient of Nb3⁺ doped Zinc Borophosphate glass were studied using Phy-X software.

Energy transfer-based color tunability, thermal quenching, and quantum yield of Sm3+/Eu3+ codoped lithium zinc borophosphate glasses

Lithium zinc borophosphate (LZBP) glasses, imbedded with Sm3+, Eu3+, & Sm3+/Eu3+ ions in solely and combinedly were synthesized using melt-quenching technique, and their energy-transfer-dependent photoluminescence (PL)-related characteristics were explored. LZBP: 0.5 % Sm3+ and LZBP: 0.5 % Eu3+ glasses exhibited intense orange and red emissions under 404 and 394 nm excitation wavelengths, respectively. When the Sm3+/Eu3+ codoped glass systems were excited with Sm3+ excitation (404 nm), has lead to a noticeable drop in the emission intensity of Sm3+ peaks at 562 nm (4G5/2 → 6H5/2; yellow), 602 nm (4G5/2 → 6H7/2, orange), and 645 nm (4G5/2 → 6H9/2, red) whereas the emission intensity of Eu3+ peaks at 591 nm (5D0→7F1; orange) and 617 nm (5D0→7F2; red) has enhanced. At the same time, the decay lifetime of singly doped Sm3+ decreased from 1.54 to 0.91 ms, with codoping different concentrations of Eu3+ ions. The decrease in both PL intensity and lifetimes of Sm3+ in the presence of Eu3+ suggests an efficient energy transfer (ET) from Sm3+→Eu3+, which is facilitated by dipole-dipole interaction. The ET from Sm3+→Eu3+ achieved through the channels, Sm3+:4G5/2 + Eu3+:7F1 → Sm3+:6H7/2 + Eu3+:5D0 and Sm3+:4G5/2 + Eu3+:7F2 → Sm3+:6H5/2 + Eu3+:5D1. Furthermore, ET from Sm3+ to Eu3+ is supported by the spectral overlay between Sm3+ emission and Eu3+ absorption, ET parameters (η(Sm3+⟶Eu3+) = 40.91 % and P(Sm3+⟶Eu3+) = 1098.9 S-1). The shift in color coordinated from orange to red, with an increase in Eu3+ doping content in the codoped glasses at 404 nm excitation demonstrates the promising application of the Sm3+/Eu3+ codoped glass system in orange-red light-emitting diodes. LZBP: 0.5 Sm3+/1.0 Eu3+ codoped glass exhibited good thermal stability (Ea = 0.19 eV), depending on temperature-dependent PL properties. The quantum yield (η) for the LZBP glass containing 0.5 Sm3+/1.0 Eu3+ codoped ions is evaluated to be 44.6 %.

Enhanced reddish-orange luminescence from Sm3+/Ag co-doped barium zinc borophosphate glasses: Structural and Judd-Ofelt analysis

We report the synthesis and optical response of Sm3+/Ag nanoparticles (NPs) co-doped glasses through melt quenching method. TEM analysis confirmed Ag NP formation, and the diverse functional groups were confirmed through FTIR studies. The Judd-Ofelt (JO) parameters are calculated using JO theory from absorption spectra. The PL spectra were recorded under 402 nm excitation and they show four PL bands in the visible range. The PL spectra are utilized to obtain radiative parameters to claim their utility in visible laser applications. The dominant emission color was obtained by using the CIE color chromaticity diagram. The excited state lifetime values were estimated through decay curve fitting method. All the obtained results are discussed in detail based on Ag NP concentrations.

Influence of Calcium Fluoride on the Radiative Properties of Sm3+ Doped Zinc Borophosphate Glasses

The borophosphate glasses compositions based on (64-x)P2O5-5B2O3-15ZnO-15Li2O-xX-1Sm2O3 (x = 0 & 15; X = CaF2) are prepared by melting and quenched technique. The optical and photoluminescence were obtained from the UV-Vis-NIR spectrophotometer and spectrofluorophotometer. The ground state 6H5/2 as the start transition in the absorption spectrum and the Judd-Ofelt intensity parameters (Ω2, Ω4, and Ω6) were determined. The emission spectra of borophosphate glass with CaF2 were recorded at an excitation of 401 nm which gave four peaks namely 6H5/2, 6H7/2, 6H9/2, and 6H11/2. The results of radiative properties for the 4G5/2 → 6H7/2 transition were found to be higher in the zinc borophosphate glass without fluoride. Based on these results, zinc borophosphate glass can be used as a candidate for the orange laser application.

Influence of Alkaline Earth Metals on the Optical Properties and Radiation-Shielding Effectiveness of Sm3+-Doped Zinc Borophosphate Glasses

Influence of Alkaline Earth Metals on the Optical Properties and Radiation-Shielding Effectiveness of Sm3+-Doped Zinc Borophosphate Glasses

The effect of ZnO on the structural and radiation shielding properties in borophosphate glasses

In this work, the influence of ZnO content in the structural and radiation shielding parameters of zinc borophosphate glass were studied. The glass batch was prepared by using the melt-quenching technique. The structural analyses have been carried out using XRD, Raman spectroscopy, 11B and 31P solid state MAS NMR. Density and glass transition temperature (Tg) were measurements and band gap were determined. XRD confirms the non-crystalline nature of the prepared samples. Changes in the structural characteristics with composition are associated with a replacement of BO4 by BO3 units and the replacement of PO4 phosphorous units by PO4−1 and PO4−2 units, leading to an increase of the average number of non-bridging oxygen (NBO). Density values revealed an increase of up to 43% and Tg shows reduction followed by stability with the replacement of P2O5 by ZnO. Band gap energies were measured as a function of ZnO content. Photon interaction parameters of the zinc borophosphate glasses have been investigated by the mass attenuation coefficient (MAC), half value layer (HVL), and mean free path (MFP). For radiation in the X-ray range (40 KeV), the MAC value for glass is 887% higher than for concrete and the HVL decreases almost four times, from 20 to 6 mm thickness, with the increase of ZnO content. The rise in ZnO content also improves all radiation attenuation parameters and the results reported here show that zinc borophosphate glasses present better results than ordinary concrete and is comparable to lead-based glasses. These characteristics make this glass system an excellent choice as a high-energy ionizing radiation attenuator.

Excitation‐dependent energy transfer and color tunability in Dy3+/Eu3+ co‐doped multi‐component borophosphate glasses

AbstractUsing the melt‐quench technique, potassium zinc borophosphate (KZnBP) glasses incorporated with Dy3+, Eu3+, and Dy3+/Eu3+ ions individually and combinedly were prepared, and their photoluminescence (PL)‐related features were investigated. The KZnBP glass containing an optimized content of Dy3+ (0.5 mol%) is co‐doped with Eu3+ in various contents, and the energy transfer (ET) process between them was studied at λexci = 349, 364, 387 (Dy3+), and 394 nm (Eu3+). The Dy3+/Eu3+ co‐doped system, when excited with Dy3+ excitations has resulted in a significant decrease in the intensity of Dy3+ peaks observed at 480 nm (4F9/2→6H15/2, blue) and 574 nm (4F9/2→6H13/2, yellow), with simultaneous enhancement of the intensity of Eu3+ peaks at 591 nm (5D0→7F1, orange) and 617 nm (5D0→7F2, red). This trend is due to the efficient energy transfer from Dy3+ to Eu3+, indicating that Eu3+ ions were sensitized by Dy3+ ions. Dexter's theory and the Inokuti–Hirayama (I–H) model revealed that the dipole–dipole interaction is accountable for the energy transfer from Dy3+ to Eu3+ through energy‐transfer channels [4F9/2(Dy3+)+7F1,2(Eu3+)→6H15/2(Dy3+)+5D2(Eu3+)] and [4F9/2(Dy3+)+7F0(Eu3+)→6H13/2(Dy3+)+5D0(Eu3+)]. The color coordinates of the Dy3+/Eu3+ co‐doped glasses under various excitations fall within the white light emission spectrum, indicating their potential application in warm white LEDs.

Structure, Judd-Ofelt analysis and spectra studies of Sm3+-doped MO-ZnO-B2O3–P2O5 (M = Mg, Ca, Sr, Ba) glasses for reddish-orange light application

In the present work, a series of Sm3+-doped MO-ZnO-B2O3–P2O5 (M = Mg, Ca, Sr, Ba) glasses were prepared. The glass structure and luminescence properties were investigated by XRD, DSC, IR, absorption spectroscopy, Judd-Ofelt theory and photoluminescence spectra. The J-O parameters of Sm3+-doped glasses follow the trend of Ω4＞Ω6＞Ω2. Under the excitation of 401 nm Xenon lamp, Sm3+-doped glasses exhibited four emissions from the transitions of 4G5/2→6HJ/2 (J = 5, 7, 9, 11) in the visible spectra. The luminous intensity of Sm3+ increases with the asymmetry in local environments and decreases with the increasing radius of the alkaline-earth cation. Among the as-prepared glass, the Sm3+-doped glass containing magnesium oxide exhibits higher values of stimulated emission cross-section (2.18 × 10−21 cm2), gain bandwidth (1.40 × 10−27 cm3), and optical gain (3.83 × 10−24 cm2). All the Sm3+-doped glasses show intense orange light in the CIE 1931 chromaticity diagram with a high color purity exceeding 99%. In addition, the time-resolved emission spectra reveal the decay process of the Sm3+ ions for the transitions 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 in the glass containing magnesium oxide. It suggests that Sm3+-doped alkaline-earth zinc borophosphate glasses could be a potential candidate for reddish-orange light-conversion fluorescent materials based on the ultraviolet light-emitting diode.

Copper-containing barium zinc borophosphate glass bandpass filters: structural and optical investigations

Copper-containing barium zinc borophosphate glass bandpass filters: structural and optical investigations

Influence of the addition of Two Transition Metal Ions to Sodium Zinc Borophosphate Glasses for Optical Applications

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Up-conversion, energy transfer and CIE analysis of Er3+/Tm3+: MCZBP glasses

Er3+-Tm3+ ions single doped and co-doped magnesium cadmium zinc borophosphate (MCZBP) glasses were prepared with melt quenching. Their density (ρ), refractive index (n), the dielectric susceptibility (χ(1)), and the nonlinear optical susceptibility (χ(3)) etc., were articulated. Up-conversion photoluminescence spectrum of Er3+ doped glass has only a strong green emission around 550 nm assigned to 4S3/2 → 4I15/2 transition, and that of Tm3+ doped glass has only a strong NIR (near infrared) emission around 820 nm corresponding to 3H4→3H6 transition, while that of Er-Tm co-doped one has both of them, of which green emission intensity almost changed little, but NIR emission intensity nearly doubled. The latter can be attributed to the efficient energy transfer from Er3+ ions to Tm3+ ions, of which mechanism was explored. The CIE chromaticity coordinates, colour purity (CP), and correlated colour temperature (CCT) parameters were also computed for all glasses and reported.

Judd-Ofelt analysis and visible luminescence of Sm3+: MCZBP glass for reddish-orange laser and multi-colour display applications

A new series of Sm3+ ions doped magnesium cadmium zinc borophosphate (Sm3+: MCZBP) glasses were prepared with melt quenching, and were characterized with X-ray diffraction, optical absorption spectra, excitation spectrum, emission spectra, and fluorescence decay curves. The increase of Sm3+ ions concentration increased the density (ρ), refractive index (n) and decreased the molar volume (Vm) of the glass. The non-metallic nature was identified from the metallization factor (M). The optical absorption spectra were used to understand the optical band gap (direct and indirect). The oscillator strength and Judd-Ofelt (JO) intensity parameters were determined from the optical absorption spectra and further used to evaluate the radiative properties of the Sm3+ ions doped glasses. The luminescence spectra showed the four emissions from transitions 4G5/2→6HJ (J = 5/2, 7/2, 9/2, and 11/2), corresponding to 562 nm (17793 cm−1), 597 nm (16750 cm−1), 644 nm (15527 cm−1) and 704 nm (14204 cm−1) upon exciting with 401 nm (24937 cm−1) wavelength, respectively. CIE chromaticity co-ordinates (x, y), the colour purity (CP), and the correlated colour temperature (CCT) values were calculated, showing that the emission colour fell in the reddish-orange region. The experimental lifetime (τexp), quantum efficiency (η), stimulated emission cross-section (σPE), gain bandwidth (σPE×Δλeff), and optical gain parameter (σPE×τexp) were articulated from the emission spectra of the glasses. The decay curves of 4G5/2 excited state exhibited non-exponential profile for all the present glasses. The efficient energy transfer between two Sm3+ ions through cross-relaxation was analysed with Inokuti-Hirayama (IH) model (S = 6). All the absorption and spectroscopic results revealed that 1SmMCZBP glass had a strong reddish-orange emission at 597 nm corresponding to 4G5/2 → 6H7/2 transition, and could be very promising material for laser and multi-colour display.

Exploration of zinc borophosphate glasses as dispersion media for SiAlON phosphors

AbstractCa‐α‐SiAlON:Eu2+ oxynitride phosphors are typical luminescent materials with high thermal tolerances. A series of zinc borophosphate glass samples (ZnO–B2O3–P2O5) were prepared to investigate their ability to disperse Ca‐α‐SiAlON:Eu2+ phosphor powders and to obtain phosphor‐in‐glass (PiG). PiG was prepared with SiAlON and zinc borophosphate glass through a melting process, and seven types of PiGs were successfully obtained without obvious degradation of SiAlON. In particular, PiGs prepared from 30ZnO–40B2O3–30P2O5 and 60ZnO–30B2O3–10P2O5 (mol%) glasses showed the highest quantum efficiency (QE). The glass structures of the mother glasses were investigated by nuclear magnetic resonance spectroscopy (NMR) and Raman spectroscopy; it was important to reduce the Q0 species of PO4 units and 4‐coordinate boron for a high QE. From the X‐ray diffraction (XRD) and scanning electron microscopy (SEM) images, it was established that ZnAl2O4 was formed around the SiAlON powders in PiG composed of the 60ZnO–30B2O3–10P2O5 (mol%) glass.

Investigation on the lithium ion dynamics in the context of microscopic length scale in zinc borophosphate glass

Dynamics of lithium ions in lithium borophosphate glass has been investigated. The mean square displacement of the lithium ions in the conduction process through the glass matrix has been estimated by using linear response theory. The lithium ions perform diffusive motion in long time scales but perform non-random correlated motion in short time scale. A new model has been proposed in the context of jump relaxation theory of K. Funke to investigate the time and temperature dependence of the mean square displacement. Experimental data can be successfully fitted with this model. Two types of activation energies such as ac activation energy and dc activation energy play a key role in ion dynamics. Perfect superposition of the mean square displacement curves at different temperatures indicates that the dynamics of the lithium ions is independent of the temperature.

Luminescence of Sn^2+ center in oxide glass with a tendency toward phase separation

Photoluminescence (PL) of Sn2+ in oxide glasses is affected by the local coordination field because of the electrons in the outermost shell. Not only the emission energy varies depending on the local coordination, but also the transparency, and it is worth examining the local distribution of Sn2+ cations in oxide glasses, which have a tendency toward phase separation, especially in an ionic (phosphate)–covalent (borate) binary system. Here, we report the structural changes in zinc borophosphate glass and the PL properties of Sn2+ in oxide glasses. The building blocks of the main glass network vary depending on the chemical composition. We found that the Sn2+ species in B2O3-rich glasses differ from those in P2O5-rich glasses, as observed in the optical absorption, PL peaks, and PL decay constants. 119Sn Mossbauer spectra indicate that isomer shifts of Sn2+ also affect the local coordination change depending on the chemical composition. According to these results for the Sn2+ center, we conclude that Sn2+ centers are homogeneously dispersed in the borophosphate network without localization around the phosphate region.

UV light induced red emission in Eu3+-doped zincborophosphate glasses

This paper reports the preparation of transparent zincborophosphate (ZBP) glasses doped with Eu3+ ions by the conventional melt quenching technique. The prepared glasses were characterized using powder XRD, FTIR, optical absorption, photoluminescence and decay curves. Judd-Ofelt (JO) intensity parameters calculated under various constraints using absorption and emission spectra. These JO intensity parameters have been used to predict the radiative properties such as radiative life time, branching ratios and stimulated emission cross section of the 5D0→7FJ (J = 0–4) transitions. Decay curves for the 5D0 level of Eu3+ ions shows single exponential for all concentrations. Luminescence properties of 5D0→7F2 transitions of Eu3+ions have revealed that the present ZBP:Eu3+ glasses have significant in optical applications at around 613 nm. An intense red luminescence has been observed due to 5D0→7F2 transition of Eu3+ ion in these glasses. From the CIE color coordinate diagram, it is observed that the present glass system is prominent material for red emission.

Study on the water durability of zinc boro-phosphate glasses doped with MgO, Fe2O3, and TiO2

The water durability of zinc boro-phosphate (PZB) glasses with the composition 60P2O5-20ZnO-20B2O3-xMeO (x = 0, 2, 4, 6 and MeO = MgO, Fe2O3, or TiO2) (mol%) was measured, and PZB glass was studied in terms of its thermal properties, density, and FTIR characteristics. The surface conditions and corrosion byproducts were analyzed using scanning electron microscopy. When MgO, Fe2O3, and TiO2 were doped into the PZB glass, Q2 was decreased and Q1 was increased in the phosphate structure, while the number of BO4 structures increased with increasing MeO content. The density of the PZB glass was increased by the addition of Fe2O3 and TiO2, while the glass transition temperature (T g ) and dilatometric softening temperature (T d ) were increased when additional MgO, Fe2O3, and TiO2 were added. From the weight loss analysis (95 ◦ C, 96 h), TiO2 doped glass showed the lowest weight loss (1.70 × 10 −3 g/cm2) while MgO doped glass showed the highest value (2.44 × 10 −3 g/cm2), compared with PZB glass (3.07 × 10 −3 g/cm2). These results were discussed in terms of the Me n+ ions in the glass structure, and their different coordination numbers and bonding strengths.

Catalytic and antibacterial activities of novel colored zinc borophosphate glasses

Colored ZBP glasses with multiple catalytic properties have been successfully synthesized using a one-step melt-quenching technique.