The dependence of luminescence on reduction of Sm2+ ions doped in lithium barium borate glasses

Sm³⁺-doped Li₂O–BaO–B₂O₃ glass was prepared by the conventional melt quenching method in air atmosphere. Sm²⁺ ions were obtained by two methods, i.e. heating the as-made glass in a reducing atmosphere and irradiating the sample under X-rays. The two obtained samples were investigated by luminescence spectra and lifetime measurements. It was found that the conversion of Sm³⁺→Sm²⁺ after X-ray irradiation is efficient in this borate glass. Photo-stability of Sm²⁺ ions was evaluated by the photo-bleaching method. Furthermore, thermo-luminescence was also measured. The different defects and the reduction mechanism of Sm²⁺ ions in this borate glass were discussed. This would be helpful to understand the reduction mechanism of Sm²⁺ ions in borate glasses.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Er<Superscript>3+</Superscript> as glass structure modifier of Ga–Ge–S chalcogenide system

Er³⁺ clustering phenomenon in Ga–Ge–S chalcogenide system is studied using Raman spectroscopy. The Raman spectra from 10 to 500 cm⁻¹ for glasses (100−y)[15Ga₂S₃–85GeS₂]–yEr₂S₃ (y=0.08−5.00 mol. %) have been analyzed. To reveal the influence of the chemical composition on the glass structure the intensity of the peak corresponding to Ge–Ge (Ga–Ga) homopolar bonds has been examined. The peak intensity increase with Er₂S₃ concentration change in the region 0<C(Er₂S₃)<2 mol. % has been interpreted in terms of the sulphur deficiency in the glass resulting in the formation of S₃Ge–GeS₃ (S₃Ga-GaS₃) structural units. The further increase in concentration beyond 2 mol. % reduces the sulphur deficiency, which can be attributed to the formation of the ternary compound Er₃GaS₆. The structural units Er₃GaS₆ contain a large mol. fraction of Er³⁺ or, in other words, Er³⁺ clusters. The data obtained from the low-frequency Raman spectra (boson band) indicate strong variations of the medium-range order (MRO) in the glasses induced by Er³⁺. The observed behavior of the MRO size (the correlation length) with increasing of Er₂S₃ concentration provides for additional evidence of the Er³⁺ clustering.     

Analysis of the optical properties of Er3+-doped strontium barium niobate nanocrystals using time-resolved laser spectroscopy

This paper reports the results obtained in strontium barium niobate (SBN) nanocrystals in glasses doped with 1, 2.5 and 5 mol% of Er³⁺ ions. The melt-quenching method was applied to fabricate the glasses with composition SrO–BaO–Nb₂O₅–B₂O₃ and further thermal treatment was used to obtain glass ceramic samples from the glass precursor. X-ray diffraction patterns confirmed the formation of SBN nanocrystals with an average size of about 50 nm in diameter. Time-resolved fluorescence spectra for the emission of Er³⁺ ions at 1550 nm have been analyzed in order to confirm the incorporation of the Er³⁺ ions into the nanocrystals. Green frequency upconversion emission under excitation at 975 nm coming from the ions in the nanocrystals has been obtained. This intense upconversion is about a factor of 500 higher than that obtained from the ions which reside in the glassy phase. Moreover, temporal evolution studies have been carried out with the purpose of determining the involved upconversion mechanism and the importance of these processes as a source of losses for the optical amplification at 1550 nm.     

Network structure and thermal property of a novel high temperature seal glass

In this study, novel glasses based on SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ system are investigated for solid oxide fuel and electrolyzer cells. The network structure evolution of the glasses with increasing B₂O₃:SiO₂ ratio was studied using Raman spectroscopy. The thermal properties of the glasses, including glass transition temperature T _g and glass softening temperature T _d , were studied using dilatometry. The thermal stability of the glasses was investigated using X-ray diffraction. The study shows that as the B₂O₃:SiO₂ ratio increases, the SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ glass micro-heterogeneity and the amount of non-bridging oxygen atoms increase. Correspondingly, the T _g of the SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ glasses changes from 635 to 775°C, and the T _d changes from 670 to 815°C. Glass thermal stability decreases with B₂O₃:SiO₂ ratio increase. The glass without B₂O₃ is thermally stable after being kept at 850°C for 200 hrs.     

Comparison of selected optical properties of oxyfluoride glass fibers doped with Er3+ and co-doped with Er3+ Yb3+

The method of manufacturing and spectroscopic evaluation of the Er³⁺ ions doped and Er³⁺–Yb³⁺co-doped SiO₂–Al₂O₃–Na₂CO₃–CaO–PbO–PbF₂ oxyfluoride glass fibers is presented in the paper. Both optically active elements erbium and ytterbium were introduced into the batch in the form of fluorides. The X-ray diffraction (XRD) technique was applied at each stage of fibers manufacturing in order to control an amorphous structure of the preforms and fibers. Optical studies of glass preforms and fibers (reflection/transmission, absorption, emission, and excited state absorption (ESA)) were directed to examine their suitability as fiber amplifiers at 1.55 μm band.     

Time Resolved Fluorescence and Energy Transfer Analysis of Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>–Er<Superscript>3+</Superscript> Triply-Doped Ba–Al-Metaphosphate Glasses for an Eye Safe Emission (1.54 μm)

This paper reports on the preparation and systematic analysis of energy transfer mechanisms in Nd³⁺–Yb³⁺–Er³⁺ co-doped new series of barium-alumino-metaphosphate glasses. The time resolved fluorescence of Nd³⁺ in triply doped Ba–Al-metaphosphate glasses have revealed that, Yb³⁺ ions could function as quite efficient bridge for an energy transfer between Nd³⁺ and Er³⁺ ions. As a result, a fourfold emission enhancement at 1.54 μm of Er³⁺ ions has been achieved through an excitation of ⁴F_5/2 level of Nd³⁺ at 806 nm for the glass having 3 mol% Yb³⁺ with an energy transfer efficiency reaching up to 94%. Decay of donor (Nd³⁺) ion fluorescence has been analyzed based on theoretical models such as direct energy transfer model (Inokuti–Hirayama) and migration assisted energy transfer models (Burshtein’s hopping and Yokota–Tanimoto’s diffusion). The corresponding energy transfer parameters have been evaluated and discussed. Primarily, electrostatic dipole–dipole (s ~ 6) interactions are found to be responsible for the occurrence of energy transfer process in theses glasses.     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Optical properties of Eu3+ and Ho3+ in fluoride glasses

Conclusions Emission and excitation spectra as well as the lifetime and the Judd-Ofelt parameters were determined for the different sites occupied by Eu³⁺ ions in a fluorzirconate glass. As has been observed in borate glasses, the Ω₄ parameter increases with the excitation energy of the⁷F₀→⁵D₀ transition, while Ω₄ is nearly constant [5, 6]. These parameters are lower than in borate glasses by a factor of close to 3. The optical properties of the Eu³⁺ ions in the studied glass appear to be dominated by only one class of sites; however, the presence of a second class of sites is possible. Efficient energy transfer from Eu³⁺ to Ho³⁺ is observed, but the energy transfer parameter does not depend appreciably on the excitation wavelength. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 4, pp. 185–190, July–August, 1995.     

Synthesis of Cr-based mixed oxides by reactive ion beam mixing of Cr/X interfaces (X=Al or Si)

The 3 keV O₂⁺\mathrm{O}_{2}^{+} reactive ion beam mixing of Cr/X interfaces (X=Al or Si) has been used to synthesize Cr-based mixed oxide thin films. The kinetics of growth, composition, and electronic structure of those films has been studied using X-ray photoelectron spectroscopy, Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and factor analysis. Initially, for low ion doses, Cr₂O₃ species are formed. Later, with increasing the ion dose, Cr₂O₃ species are first transformed into Cr³⁺–O–X species, and subsequently, those Cr³⁺–O–X species are transformed into Cr⁶⁺–O–X species. This sequential transformation, Cr₂O₃→Cr³⁺–O–X→Cr⁶⁺–O–X, is accompanied by a slight increase of the oxygen concentration and a decrease of the Cr/X ratio in the films formed leading to the synthesis of custom designed Cr-based mixed oxides. The changes observed in the valence band and Auger parameters further support the formation of Cr–X mixed oxide species. Angle resolved X-ray photoelectron spectroscopy shows that for low ion doses, when only Cr₂O₃ and Cr³⁺–O–X species coexist, Cr³⁺–O–X species are located nearer the surface than Cr₂O₃ species, whereas for higher ion doses, when only Cr³⁺–O–X and Cr⁶⁺–O–X species coexist, the Cr⁶⁺–O–X species are those located nearer the surface.     

A neutron and x-ray diffraction investigation of intermediate range structure in silver borate glasses

The ion diffusion mechanism in ion conducting glasses has in many reports been suggested to be linked to the structure. However, in most cases the structures of the glasses are not very well known. We have investigated the structure of the glass system (AgI)_x (Ag₂O-2B₂O₃)_1−x, with x=0, 0.6 by neutron and x-ray diffraction experiments. AgI doping produces an intense peak in the neutron data at an anomalously low Q-value (0.8 Å⁻¹) that indicates increased intermediate range ordering. Only a weak peak is observed at a similar Q-value in the x-ray structure factor. By comparing the different neutron and x-ray weighting factors the origin of the anomalous peak is unambiguously attributed to correlations within the B-O network. The experimental results have been used to model the glasses by Reverse Monte Carlo simulations to obtain more detailed views of the structures. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Reference electrode formation in potentiometric CO2 sensors with alkali ion conducting alumosilicate glasses as solid electrolytes

Potentiometric CO₂ gas sensors with Li conducting glasses/glass ceramics of the system Li₂O-Al₂O₃-SiO₂ (different nominal composition) as solid electrolytes have been investigated. Li₂CO₃ was used as CO₂ and O₂ sensitive auxiliary electrode. During the sensor test measurements, the CO₂ partial pressure was varied between 1×10⁻³ and 1×10⁻¹ bar at a constant O₂ partial pressure of 2.1×10⁻¹ bar whereas N₂ was used as carrier gas. Comparative measurements were accomplished with sensors comprising Na and K ion conducting glasses. A metastable reference electrode was formed at the contact zone between the Au metal electrode and the former Li glasses of definite nominal composition by crystallization processes taking place, which lead to stable, reproducible CO₂ dependent EMF signals for more than 90d. The thermodynamically expected EMF difference and the observed EMF difference agree quite well between 500 and 600 °C. At 600 °C, the drift of sensors with glasses as solid electrolytes and direct Au glass/glass ceramics contact as reference electrode amounts typically 0.32 mV/d (p(CO₂)=1×10⁻³ bar, p(O₂)=2.1×10⁻¹ bar at the measuring electrode), if a metastable multiphase equilibrium is formed. At identical partial pressures of CO₂ and O₂, the signal reproducibility of these sensors with different solid electrolyte glasses of the same nominal composition lies within 30 mV at 600 °C. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Influence of Thermal Treatment on the Structure of Granitoid-Based Glasses

The processes of initiated crystallization of natural granitoid-based glasses containing FeO+Fe₂O₃ (7–8 wt.%) have been investigated by means of IR spectroscopy. It has been established that iron oxides play an active role in crystallization and pass from a disordered vitreous component into an ordered crystal one. A conclusion on the exact likeness of the processes of glass crystallization in single- and double-stage regimes of thermal treatment has been drawn. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 640–643, September–October, 2005.     

Preparation of sol-gel method P2O5-Al2O3-SiO2 glasses and their characterization

Nanostructures P₂O₅-Al₂O₃-SiO₂ glasses were prepared by sol-gel method. The glasses were characterized by XRD, FTIR and TG/DTA methods. The average pore size of the glass was less than 3 nm as measured by N₂ adsorption — desorption method. The thermal stability was measured as a function of decomposition temperature and weight loss calculations. Proton conductivities of all samples increased with an increase in relative humidity (40–90 %), indicating that continuous paths suitable for proton conduction were developed when glasses heat treated at 300 °C due to the adsorption of water. The temperature dependence of the conductivity for all compositions increases with increasing temperature in the range 30–90 °C with relative humidity 70 %. The overall conductivity was in the range 10⁻⁴–10⁻³ S/cm for compositions.     

Nonlinearity of refractive index in glasses based on heavy metal oxides with different lead and tellurium contents

We have studied the nonlinearity of the refractive index at a wavelength of 1.08 μm for optical lead silicate and lead phosphate tellurite glasses of different compositions. We have shown that the nonlinear refractive index n₂ increases as the lead content increases in lead silicate glasses and as the tellurium content increases in lead phosphate tellurite glasses, where the latter are typically have higher values of n₂, as high as 24·10⁻¹³ cgs units (47·10⁻¹⁶ cm²/W), and lower Rayleigh losses. We have established a correlation between the nonlinear refractive index and the microstructure of the studied glasses. The highly nonlinear glasses are distinguished by extensive fluctuations in the heavy metal oxide concentration which are “frozen” during cooling of the glass melt. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 780–784, November–December, 2007.     

Spectroscopic characteristics of activated tungsten phosphate glasses in the VUV region

Absorption, reflection, excitation, and quantum yield spectra of the luminescence of Eu³⁺-activated tungsten phosphate glasses were investigated within the range 30,000–95,000 cm⁻¹. It is shown that the differences between the ligands in the first coordination sphere of tungsten and the effects of their mutual influence are responsible for the appearance of tungsten groups WO ₂ ²⁺ with an increased multiplicity of the tungsten—oxygen bond. The spectroscopic properties of tungsten complexes are associated with electron transitions from three completed orbitals that have the character of transitions with charge transfer from the ligands to the coordinating center. This leads to a kind of localization of excitation in the WO ₂ ²⁺ group and ensures constancy of the quantum yield of luminescence in a wide spectral range. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 433–435, July–August, 2000.     

Blue light emission from Eu ions in sol-gel-derived Al2O3-SiO2 glasses

Blue light-emitting glasses were successfully prepared by doping Eu²⁺ ions in the system Al₂O₃-SiO₂. The Al₂O₃-SiO₂ glasses doped with Eu³⁺ ions were synthesized using a sol-gel method, followed by heating in hydrogen gas atmosphere to reduce into the Eu²⁺ ions. The obtained glasses exhibited emission spectra with peak at ∼450 nm due to 4f⁶5d→4f⁷ (⁸S_7/2) transition, the intensities of which strongly changed depending on their glass composition and heating conditions. The emission quantum efficiency of 48% was achieved by heating the glass with the ratio of Al³⁺ to Eu³⁺ at about 6 at 1000 °C in hydrogen gas atmosphere. It was found that the Al₂O₃-SiO₂ glasses were appropriate not only for homogeneously doping the Eu³⁺ ions in glass structure but also reducing to Eu²⁺ ions, resulting in enhanced blue light-emission properties.     

Upconversion emission in Er<Superscript>3+</Superscript>-doped lead niobium germanate thin-film glasses produced by pulsed laser deposition

Thin films of Er³⁺-doped lead–niobium germanate have been produced by pulsed laser deposition from Er³⁺-doped 25PbO₂–25Nb₂O₅–50GeO₂ (mol%) transparent glasses with an Er content in the range 0.5–3 wt%. The room-temperature infrared to visible upconversion properties of these thin films have been investigated under 800-nm laser excitation. An energy transfer upconversion mechanism has been identified to be responsible for the population of the ⁴S_3/2:²H_11/2 excited level, from which an intense green emission occurs. A rate equation analysis supports the proposed mechanism.     

Enhanced Green Emission from Er<Subscript>2</Subscript>WO<Subscript>6</Subscript> Nanocrystals Embedded Composite Tellurite Glasses

A series of tungsten-tellurite glasses activated with different concentrations (0–1.5 mol %) of Er³⁺ has been synthesized. The structural properties of the best luminescent sample and the optical properties of its Er³⁺ ions, are studied both immediate after its preparation as well as after its ageing. On ageing the glass suffers structural reorganization and generates Er₂WO₆—nanocrystals in the matrix, which greatly enhances the normal and upconversion green luminescence efficiency of Er³⁺. The nanocrystal aided enhancement of normal and upconversion luminescence of Er³⁺ of the glass has been attributed to the crystal field effects of the new environment of Er³⁺ in the nanocrystals. A phenomenon of preferential enhancement of red upconversion luminescence at the cost of green upconversion luminescence of Er³⁺ at its higher concentrations in the glass has been observed and the related photo-physics is proposed. The material shows the prospect of being used as NIR solar concentrator.     

Luminescence of Ln3+ and WO 2 2+ ions in wolframylphosphate glasses

We investigate the luminescent properties of potassium wolframylphosphate glasses doped with Eu³⁺, Tb³⁺, and Dy³⁺ ions whose luminescence is excited by donor-acceptor interaction between the active WO ₂ ²⁺ and Ln³⁺ ions, as well as the migration of energy in the subsystems of each type of the active ions. Comparison of the obtained data with the results of investigation of the spectroscopic properties of Ln³⁺ in uranylphosphate materials shows that a sufficiently high degree of the ionicity of bonds of Ln³⁺ with the atoms of its first coordination sphere is preserved in wolframylphosphate matrices. We show that three stages of the decomposition of electron excitations are typical of the WO ₂ ²⁺ ions in wolframylphosphate glasses doped with Ln³⁺ and two stages in nonactivated glasses. The electron excitation energy transfer in the WO ₂ ²⁺ −Ln³⁺ system occurs due to induction-resonance interaction. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 620–625, September–October, 1997.