Physical,optical and radiative properties of CaSO4–B2O3–P2O5 glasses doped with Sm3+ ions

Trivalent rare earth ions doped borosulfophosphate glasses are in high demand owing to their several unique attributes that are advantageous for applications in diverse photonic devices. Thus, Sm³⁺ ion doped calcium sulfoborophosphate glasses with composition of 25CaSO₄–30B₂O₃–(45?x)P₂O₅–xSm₂O₃ (where x?=?0.1, 0.3, 0.5, 0.7 and 1.0 mol%) were synthesized using melt-quenching technique. X-ray diffraction confirmed the amorphous nature of the prepared glass samples. Differential thermal analyses show transition peaks for melting temperature, glass transition and crystallization temperature. The glass stability is found in the range 91?°C to 116?°C which shows increased stability with addition of Sm₂O₃ concentration. The Fourier transform infrared spectral measurements carried out showed the presence of vibration bands due to PO linkage, BO_3, BO₄, PO₄, POP, OPO, SOB, and BOB unit. Glass density showed increase in value from 2.179 to 2.251?g cm^?3 with increase in Sm₂O₃ concentration. The direct, indirect band gap and Urbach energy calculated were found to be within 4.368–4.184?eV, 3.641–3.488?eV and 0.323–0.282?eV energy ranges, respectively. The absorption spectra revealed ten prominent peaks centered at 365, 400, 471, 941, 1075, 1228, 1375, 1477, 1528 and 1597?nm corresponding to ⁴D_3/2,⁶H_5/2→⁴I_11/2,⁶P_3/2, ⁶F_11/2, ⁶F_9/2, ⁶F_7/2, ⁶F_5/2, ⁶F_3/2, ⁶H_15/2 and ⁶F_1/2 transitions respectively. Photoluminescence spectra monitored at the excitation of 398?nm exhibits four emission bands positioned at 559, 596,643 and 709?nm corresponding to ⁴G_5/2→⁶H_5/2, ⁶H_7/2, ⁶H_9/2 and ⁶H_11/2 transitions respectively. The nephelauxetic parameters calculated showed good influence on the local environment within the samarium ions site and the state of the SmO bond. The Judd–Ofelt intensity parameters calculated for all glass samples revealed that Ω_6?>?Ω_4?>?Ω₂. The emission cross-section and the branching ratios values obtained for ⁴G_5/2→⁶H_7/2 transition indicate its suitability for LEDs and solid-state laser application.     

FTIR structural investigation of gamma irradiated BaO–Na2O–B2O3–SiO2 glasses

Fourier transform infrared (FT-IR) spectra of xBaO–15Na₂O–(70−x)B₂O₃–15SiO₂ glass system with x=0, 5, 10, 15 and 20 (mol%) has been measured in the spectral range 400–4000 cm⁻¹ at room temperature in order to understand the characteristic frequencies of the chemical bonds and bonding mechanisms, which are susceptible to the structural and spectral changes. The effect of gamma irradiation in the dose range 0.1 kGy–60 kGy on the infrared absorption spectra of these glasses is also reported. The change in the glass structure due to the effect of composition is also discussed. It has been observed that irradiation of the glasses with the gamma rays increases the BO₃ groups and the non bridging oxygens which make the network loose.     

Optical,physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Glasses in the compositions (Li₂O)₂₅–(BaO)₂₅–(P₂O₅)_50−x–(V₂O₅)_x (with x=0.5,1.0,1.5,2.0,2.5, and 3.0 mol%) have been prepared by the conventional melt quenching technique. X-ray powder diffractrogram show broad peaks which conforms glassy nature of the sample. Differential scanning calorimetry (DSC) thermograms show characteristic glass transition temperature (T_g) and it increases with increasing substitution of V₂O₅ for P₂O₅. The measured physical parameters like density, refractive index, ionic concentration and electronic polarizability are found to vary linearly with increasing x. Infrared spectra exhibits few bands, which are attributed to (P=O)_AS, (P=O)_S, (V=O), (P–O–P)_AS,P–O–V, (P–O–P)_AS and O–P–O vibrations. The optical absorption spectra of VO²⁺ ions in these glasses show three bands and are assigned to the ²B₂→ ²E,²B₂→ ²B₁ and ²B₂→ ²A₁ transitions. Electron paramagnetic resonance spectra of all the glass samples exhibit resonance signals characteristic of VO²⁺ ions. The values of Spin-Hamiltonian parameters indicate that the VO²⁺ ions are present in octahedral sites with tetragonal compression and belong to C_4V symmetry.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

Broadband near-IR emission and temperature dependence in Er/Tm co-doped Bi2O3–SiO2–Ga2O3 glasses

The broadband near-IR emission has been investigated in a series of Er/Tm co-doped Bi₂O₃–SiO₂–Ga₂O₃ (BSG) glasses with 800 nm laser diode as an excitation source. A broadband emission extending from 1350 to 1650 nm with a full width at half maximum (FWHM) around 165 nm is obtained in 0.2 wt% Er₂O₃ and 1.0 wt% Tm₂O₃ co-doped BSG glass. The fluorescence decay curves of glasses are measured and maximum energy transfer efficiency from Er³⁺ to Tm³⁺ reaches 71% when Tm³⁺ concentration is 1.0 wt%. The temperature dependence of the broadband emission spectra in Er³⁺–Tm³⁺ co-doped BSG glass is also recorded to further understand the energy-transfer processes between Er³⁺ and Tm³⁺. The present work suggests that Er/Tm co-doped BSG glasses can be a potential candidate for broadband integrated amplifier.     

Nonlinear optical properties of 75TeO2－20Nb2O5－5ZnO glasses doped with CeO2

Nonlinear optical properties of 75TeO_2－20Nb_2O_5－5ZnO glasses doped with CeO_2 have been investigated with a self-diffracted time-resolved degenerate four-wave mixing (DFWM) technique at different excitation intensities and lattice temperatures. The DFWM signal exhibits three peaks at higher excitation intensities, where a main peak appears at zero delay time and two rather weak side peaks are located symmetrically at the negative and positive time delay. Due to destructive interferences between the fifth- and third-order polarizations, the line-shape of the main peak around the zero time delay evolves from single peak into a double-peak structure with increasing excitation intensity. Two side peaks emerge at the positive and negative time delay and gradually intensify with increasing excitation intensity or lattice temperature, and their positions are independent of the pulse duration, temperature and excitation intensity, which are attributed to the many-body Coulomb interaction.     

Magnetic and structural properties of CaO–SiO2–P2O5–Na2O–Fe2O3 glass ceramics

Magnetic properties of glass ceramics derived from glasses with composition 41CaO·(52−x)SiO₂·4P₂O₅·xFe₂O₃·3Na₂O (2?x?10 mol% iron oxide (Fe₂O₃)) are reported. Structural investigation revealed the presence of nanocrystalline magnetite phase in the heat-treated samples containing x?2 mol% Fe₂O₃. Magnetic hysteresis cycles of the glass-ceramic samples were obtained with a maximum applied field of ±20 kOe as well as a low field of ±500 Oe, in order to evaluate the potential of these glass ceramics for hyperthermia treatment of cancer. Samples with x>2 mol% of iron oxide exhibited magnetic behavior similar to soft magnetic materials with low coercivity. The evolution of magnetic properties in these samples as a function of iron oxide molar concentration is correlated with the amount and crystallite size of magnetite phase present in them.     

Preparation and characteristics of?a?BaO–Al2O3–B2O3–SiO2–La2O3 glass ceramic via spray pyrolysis

The characteristics of a BaO–Al₂O₃–B₂O₃–SiO₂–La₂O₃ glass ceramic prepared by spray pyrolysis were studied. Glass powders with spherical shape and amorphous phase were prepared by complete melting at a preparation temperature of 1 500°C. The mean size and geometric standard deviation of the powders prepared at the temperature of 1 500°C were 0.6 μm and 1.3. The glass powders had similar composition to that of the spray solution. The glass transition temperature (T _g) of the glass powders was 600.3°C. Two crystallization exothermic peaks were observed at 769.3 and 837.8°C. Densification of the specimen started at a sintering temperature of 600°C, in which Ba₄La₆O(SiO₄)₆ as main crystal structure was observed. Complete densification of the specimen occurred at a sintering temperature of 800°C. The specimens sintered at temperatures above 800°C had main crystal structure of BaAl₂Si₂O₈.     

A comparison of electronic structure and optical properties between N-doped β-Ga2O3 and N-Zn co-doped β-Ga2O3

The electronic structure and optical properties of N-doped β-Ga₂O₃ and N-Zn co-doped β-Ga₂O₃ are investigated by the first-principles calculation. In the N-Zn co-doped β-Ga₂O₃ system, the lattice parameters of a, b, c, V decrease and the formation energy of N-Zn co-doped β-Ga₂O₃ is smaller in comparison with N-doped β-Ga₂O₃. There are two shallower acceptor impurity levels in N-Zn co-doped β-Ga₂O₃. Comparing with N-doped β-Ga₂O₃, the major absorption peak is red-shifted and the impurity absorption edge is blue-shifted for N-Zn co-doped β-Ga₂O₃. The results show that the N-Zn co-doped β-Ga₂O₃ is found to be a better method to push p-type conductivity in β-Ga₂O₃.     

Biomolecule-assisted hydrothermal synthesis of Sb2S3 and Bi2S3 nanocrystals and their elevated-temperature oxidation behavior for conversion into α-Sb2O4 and Bi2O3

We have developed a novel biomolecule-assisted hydrothermal method to prepare Sb₂S₃ and Bi₂S₃ nanocrystals with various sizes and shapes, in which cysteine combined with other sulfur source can exert the synergistic effect on products. The samples were characterized XRPD, TEM, HRTEM, FESEM, and PL techniques. First, we prepared a series of Sb₂S₃ and Bi₂S₃ nanocrystals by simply adjusting the composition of sulfur sources under hydrothermal conditions. Then, we studied the elevated-temperature oxidation behavior of these sulfides in air, which can lead to the formation of α-Sb₂O₄ and Bi₂O₃ samples at 600 °C for 3 h. The optical properties of the α-Sb₂O₄ and Bi₂O₃ samples were also discussed.     

Glass formation and physical properties of Sb2S3–CuI chalcogenide system

Novel chalcogenide glasses of pseudo-binary(100-x)Sb₂S_3-xCuI systems were synthesized by traditional meltquenching method.The glass-forming region of Sb₂S₃-CuI system was determined ranging from x=30 mol% to 40 mol%.CuI acts as a non-bridging modifier to form appropriate amount of [SbSI] structural units for improving the glass-forming ability of Sb₂S₃.Particularly,as-prepared glassy sample is able to transmit light beyond 14 μm,which is the wider transparency region than most sulfide glasses.Their physical properties,including Vickers hardness(Hv),density(ρ),and ionic conductivity(σ) were characterized and analyzed with the compositional-dependent Raman spectra.These experimental results would provide useful knowledge for the development of novel multi-spectral optical materials and glassy electrolytes.     

Optical,thermal, and structural properties of Nb2O5–TeO2 and WO3–TeO2 glasses

Glass samples from two systems, Nb₂O₅–TeO₂ and WO₃–TeO₂, were prepared at two melt quenching rates and characterized by density, DSC, UV-visible, and Raman spectroscopy. Addition of Nb₂O₅ decreased the density while increase in the WO₃ concentration increased the density. Glasses prepared at higher quenching rates had smaller densities than glasses of the same composition prepared at lower quenching rate although the short-range structure of both glasses were identical, as revealed by Raman spectroscopy. Optical studies found an intense absorption band just below the absorption edge in both the glass series. This band was attributed to electronic transitions of Nb⁵⁺ and W⁶⁺ ions and a lone pair of electrons on Te atoms. Glass transition temperature increased with increase in Nb₂O₅ and WO₃ mol% due to the increase in average bond strength in the glass network. Raman spectroscopy showed that the concentration of TeO₄ units decreased with the increase in Nb₂O₅ and WO₃ concentrations.     

Preparation and spectral characterization of new Er3+-doped TeO2－B2O3－WO3－ZnO－ZnS glasses

Erbium-doped TeO_2-based oxysulfide glasses have been prepared in argon atmosphere in graphite crucibles. The results of thermal analysis and spectroscopic properties of Er^{3+} have been studied in terms of sulfide influence. As a function of composition, we have measured principally the optical absorption, spontaneous emission, and lifetime of the materials. Judd－Ofelt theory was introduced to calculate bandwidth and emission cross-section of Er^{3+}. The results demonstrate that addition of sulfide in tellurite glasses results in broad emission spectra, with high emission cross-section, slightly low emission lifetime and a comparatively high thermal stability as pure oxide glasses.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.     

Effects of N-doping concentration on the electronic structure and optical properties of N-doped β-Ga2O3

The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most stable structure for the smallest formation energy.After N-doping,the charge density distribution significantly changes,and the acceptor impurity level is introduced above the valence band and intersects with the Fermi level.The impurity absorption edges appear to shift toward longer wavelengths with an increase in N-doping concentration.The complex refractive index shows metallic characteristics in the N-doped β-Ga2O3.     

Electronic and thermodynamic properties of α-Pu2O3

Based on density functional theory+U$\text{density functional theory}+U$ calculations and the quasi-annealing simulation method, we obtain the ground electronic state for α-Pu₂O₃ and present its phonon dispersion curves as well as various thermodynamic properties, which have seldom been theoretically studied because of the huge unit cell. We find that the Pu–O chemical bonding is weaker in α-Pu₂O₃ than in fluorite PuO₂, and subsequently a frequency gap appears between oxygen and plutonium vibration density of states. Based on the calculated Helmholtz free energies at different temperatures, we further study the reaction energies for Pu oxidation, PuO₂ reduction, and transformation between PuO₂ and α-Pu₂O₃. Our reaction energy results are in agreements with available experiment. And it is revealed that high temperature and insufficient oxygen environment are in favor of the formation of α-Pu₂O₃.     

Microwave synthesis, characterization, and electrochemical properties of α-Fe2O3 nanoparticles

Ultrafine α-Fe₂O₃ nanoparticles with an extremely narrow distribution were synthesized by microwave heating. Transmission electron microscopy (TEM) images showed that most primary particles have ellipsoid shapes, and the average diameter of the primary particles was less than 10 nm. The electron diffraction pattern and fringes in some particles in TEM images showed that these nanoparticles were single crystals. The BET surface area of the freeze-dried product was 217 m²/g. The initial discharge capacity of the α-Fe₂O₃ nanoparticles exceeded 1007 mA/g (cut-off voltage: 0.5 V). This large capacity corresponds to that calculated by assuming the reduction of Fe³⁺ to Fe⁰. The α-Fe₂O₃ nanoparticles also work as a rechargeable electrode material. The charge-discharge test between 4 V and 1.5 V gave a good rechargeable capacity of about 150 mAh/g.     

Structure, electrical properties and temperature characteristics of?Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–Bi0.5Li0.5TiO3 lead-free piezoelectric ceramics

(1−x−y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃– yBi_0.5Li_0.5TiO₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique, and their structure, electrical properties, and temperature characteristics have been studied systematically. The ceramics can be well-sintered at 1050–1150 °C. The increase in K⁺ concentration decreases the grain-growth rate and promotes the formation of grains with a cubic shape, while the addition of Li⁺ decreases greatly the sintering temperature and assists in the densification of BNT-based ceramics. The results of XRD diffraction show that K⁺ and Li⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. As x increases from 0.05 to 0.50, the ceramics transform gradually from rhombohedral phase to tetragonal phase and consequently a morphotropic phase boundary (MPB) is formed at 0.15≤x≤0.25. The concentration y of Li⁺ has no obvious influence on the crystal structure of the ceramics. Compared with pure Bi_0.5Na_0.5TiO₃, the partial substitution of K⁺ and Li⁺ for Na⁺ lowers greatly the coercive field E _c and increases the remanent polarization P _r of the ceramics. Because of the MPB, lower E _c and large P _r, the piezoelectricity of the ceramics is improved significantly. For the ceramics with the compositions near the MPB (x=0.15–0.25 and y=0.05–0.10), the piezoelectric properties become optimum: piezoelectric coefficient d ₃₃=147–231 pC/N and planar electromechanical coupling factor k _P=20.2–41.0%. In addition, the ceramics exhibit relaxor characteristic, which probably results from the cation disordering in the 12-fold coordination sites. The depolarization temperature T _d shows a strong dependence on the concentration x of K⁺ and reaches the lowest values at the MPB. The temperature dependences of the ferroelectric and dielectric properties at high temperatures may imply that the ceramics may contain both the polar and non-polar regions at temperatures above T _d.