Thermal and optical properties of Tm3+ doped tellurite glasses

Ultraviolet, visible (UV/VIS) and differential thermal analysis (DTA) measurements were carried out in order to investigate the optical and thermal properties of various 0.5 mol.% Tm2O3 containing (1 - x)TeO2 + xLiCl glasses in molar ratio. The samples were prepared by fusing the mixture of their respective reagent grade powders in a platinum cricuble at 750 degrees C for 30 min. DTA curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while melting was not observed for the glasses containing LiCl content less than 50 mol.%. These glasses were found to be moisture-resistant. However, the glasses with LiCl content higher than 50 mol.%, in which a melting peak was observed at Tc = 401 degrees C, were moisture-sensitive. Absorption measurements in the UV/VIS region of the glasses without Tm2O3 content show that the Urbach cutoff occurs at about 320 nm and, is relatively independent of the LiCl content. Six absorption bands were observed in the Tm2O3 doped glasses corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of Tm3+ ions. The spectra also show that the integrated absorption cross-section of each band depends on the glass composition. Judd-Ofelt theory was used to determine the Judd-Ofelt parameters as well as the radiative transition probabilities for the metastable levels of Tm3+ ions in (0.3)LiCl + (0.7) TeO2: 0.01 Tm2O3 glass which is moisture-resistant.     

Study of EPR, optical properties and electrical conductivity of vanadyl doped Bi2O3.PbO.B2O3 glasses

Heavy metal based oxide glasses having composition xBi(2)O(3).(0.30 - x)PbO.0.70B(2)O(3) have been prepared (0.00 < or = x < or = 0.15, mol%) containing 2.0mol% of V(2)O(5) by normal melt-quenching technique. Electron paramagnetic resonance (EPR), optical spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHP) of VO(2+) ions, dipolar hyperfine parameter, P and Fermi contact interaction parameter, K, molecular orbital coefficients (alpha(2) and gamma(2)) and optical band gap have been calculated. It is observed that in these glasses, the tetragonal nature of V(4+)O(6) complex increases with Bi(2)O(3) content. Increase in Bi(2)O(3):PbO ratio results in the contraction of 3d(xy) orbit of the unpaired electron in the vanadium ion, and the SHP are dependent on the theoretical optical basicity, Lambda(th). In present glasses, the conductivity (activation energy) first decreases (increases) with increase in mol% of Bi(2)O(3) content upto x = 0.08 and then shows a maxima (minima) at x = 0.10 and then starts decreasing (increasing) upto x < or = 0.15 with mol% of Bi(2)O(3) content.     

Optical absorption and photoluminescence properties of Er3+ doped mixed alkali borate glasses

An investigations of the optical absorption and fluorescence spectra of 0.2 mol% Er2O3 in mixed alkali borate glasses of the type 67.8B2O3 x xLi2O(32-x)Na2O, 67.8B2O3 x xLi2O(32-x)K2O and 67.8B2O3 x xNa2O(32-x)K2O (where x = 8, 12, 16, 20 and 24) are presented. The glasses were obtained by quenching melts consisting of H3BO3, Li2CO3, Na2CO3, K2CO3 and Er2O3 (950-1100 degrees C, 1.5-2 h) between two brass plates. Spectroscopic parameters like Racah (E1, E2 and E3), spin-orbit (xi(4f)) and configuration interaction (alpha) parameters are deduced as function of x. Using Judd-Ofelt theory, Judd-Ofelt intensity parameters (omega2, omega4 and omega6) are obtained. Radiative and non-radiative transition rates (A(T) and W(MPR)), radiative lifetimes (tauR), branching ratios (beta) and integrated absorption cross-sections (sigma) have been computed for certain excited states of Er3+ in these mixed alkali borate glasses. Emission spectra have been studied for all the three Er3+ doped mixed alkali borate glasses. The present paper throws light on the trends observed in the intensity parameters, radiative lifetimes, branching ratios and emission cross-sections as a function of x in these borate glasses, keeping in view the effect of mixed alkalies in borate glasses.     

Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3-ZnO-PbO glasses

This paper reports on the spectral properties of Mn2+, Co2+ and Ni2+ ions doped B2O3-ZnO-PbO glasses. XRD, FT-IR spectra and DSC profiles of these glasses have also been carried out, and the FT-IR profiles have shown the presence of both BO3 and BO4 units. It is interesting to notice that the FT-IR peak positions are slightly shifted towards higher energy with an increase in transition metal ion concentration change. From the measured DSC thermograms, glass transition (T(g)), crystallization (T(c)) and temperature of melting (T(m)) have been evaluated. From the UV absorption spectra of Mn2+, Co2+ and Ni2+ ions doped glasses, both direct and indirect optical band gaps have been calculated. The visible absorption spectra of Mn2+:glasses have shown a broad absorption band at 520 nm (6A1g(S) --> 4T1g(G)); with Co2+ ions one absorption band at 605 nm (4A2(4F) --> 4T1(4P)) and another at 1450 nm (4A2(4F) --> 4T1(4F)); and for Ni2+:glasses three absorption bands at 420 nm (3A2g(F) --> 3T1g(P)), 805 nm (3A2g(F) --> 1Eg(D)) and 880 nm (3A2g(F) --> 3T1g(F)) have been observed. For Mn2+:glasses, upon excitation with 262 nm, a green emission (539 nm) with a slight blue shift; and with 392 nm, a green emission (534 nm) with a slight red shift with Mn2+ ions concentration change (0.2-0.5 mol%) has been observed. This green emission has been assigned to (4T1(G) --> 6A1(S)) d-d transition of Mn2+ ions that are in tetrahedral co-ordination. For 0.5 mol% Co2+ ions doped glass, upon excitation with 580 nm, a red emission (625 nm) has been observed which originates from 2E(2G) --> 4A2(4F) transition of Co2+ ions in tetrahedral co-ordination. For Ni2+ ions doped glasses upon excitation with 420 nm, a green (577 nm) and red (670 nm) emissions are observed and are assigned to (1T2g(D) --> 3A2g(F)) and (1T2g(D) --> 3T2g(F)) d-d transitions of Ni2+ ions in octahedral co-ordination.     

Effects of gamma irradiation on optical and structural properties of PbO–Bi2O3–B2O3 glasses

Optical and structural properties of xPbO·2xBi₂O₃(1−3x)B₂O₃ glasses of different composition have been studied using UV-VIS and FTIR spectroscopic techniques. Effects of gamma radiations on glass network and structural units have been studied by irradiating glass samples with a ⁶⁰Co radioisotope to the overall dose of 2.5 kGy. It is shown that irradiation causes compaction of the borate network by breaking the bonds between trigonal elements, which leads to a decrease in the optical band gap energy. Changes in the atomic structure before and after the irradiation are observed and explained.     

Effect of Bi2O3 on spectroscopic and structural properties of Er3+ doped cadmium bismuth borate glasses

Glasses with composition 20CdO·xBi(2)O(3)·(79.5-x)B(2)O(3) (15≤x≤35, x in mol%) containing 0.5 mol% of Er(3+) ions were prepared by melt-quench technique (1150°C in air). The amorphous nature of the glasses was confirmed by X-ray diffraction. The spectroscopic properties of the glasses were investigated using optical absorption spectra and fluorescence spectra. The phenomenological Judd-Ofelt intensity parameters Ω(λ) (λ=2, 4, 6) were determined from the spectral intensities of absorption bands in order to calculate the radiative transition probability (A(R)), radiative life time (τ(R)), branching ratios (β(R)) for various excited luminescent states. Using the near infrared emission spectra, full width at half maxima (FWHM), stimulated emission cross-section (σ(e)) and figure of merit (FOM) were evaluated and compared with other hosts. Especially, the numerical values of these parameters indicate that the emission transition (4)I(13/2)→(4)I(15/2) at 1.506 μm in Er(3+)-doped cadmium bismuth borate glasses may be useful in optical communication.     

Effect of B2O3 on luminescence of erbium doped tellurite glasses

The B2O3 was introduced into the Er3+ doped TeO2-ZnO-Na2O glass to increase the phonon energy of the host. The effect of B2O3 on the non-radiative rate of the 4I11/2-->4I13/2 transition of Er3+, the lifetime of the 4I11/2 and 4I13/2 levels, the green and red upconversion emissions intensity, and the 4I13/2-->4I15/2 emission intensity was discussed. The results show that the phonon energy of boro-tellurite glass is close to that of germanate glass and is quite smaller than that of borate glass. The lifetime of 4I11/2 level and the upconversion emissions decrease with increasing B2O3 concentration. The higher OH group concentration presented in the boro-tellurite glass may shorten the lifetime of 4I13/2 level and also reduce the quantum efficiency of 4I13/2-->4I15/2 emission. The future dehydrating procedures are suggested to enhance the efficiency of amplification at 1.5 microm band.     

Preparation and Electrochemical Properties of xLi2MnO3·(1-x)LiMn2O4 Composites

Li₂MnO₃-doped spinel LiMn₂O₄ composites were synthesized by sol-gel method to improve the electrochemical performance of LiMn₂O₄. The microstructures, morphologies and electrochemical performance of the obtained xLi₂MnO₃·(1-x)LiMn₂O₄ composites were characterized by X-ray diffraction(XRD), scan electron microscopy(SEM) and a galvanostatic charge-discharge process. It was found that both Li₂MnO₃ and LiMn₂O₄ components exist in xLi₂MnO₃·(1-x)LiMn₂O₄(02MnO₃·0.7LiMn₂O₄ composite shows the optimized electrochemical performance, including discharge capacity and cycle stability. It was demonstrated that Li₂MnO₃-doped spinel LiMn₂O₄ cathode material can work at wide potential window with quite good capacity retention and considerably larger reversible capacity compared to single-phase LiMn₂O₄ component.     

Enhancement of luminescence properties in Er3+ doped TeO2-Na2O-PbX (X=O and F) ternary glasses

An enhancement of luminescence properties in Er3+ doped ternary glasses is observed on the addition of PbO/PbF2. The infrared to visible upconversion emission bands are observed at 410, 525, 550 and 658 nm, due to the 2H9/2-->4I15/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 transitions respectively, on excitation with 797 nm laser line. A detailed study reveals that the 2H9/2-->4I15/2 transition arises due to three step upconversion process while other transitions arise due to two step absorption. On excitation with 532 nm radiation, ultraviolet and violet upconversion bands centered at 380, 404, 410 and 475 nm wavelengths are observed along with one photon luminescence bands at 525, 550, 658 and 843 nm wavelengths. These bands are found due to the 4G11/2-->4I15/2, 2P3/2-->4I13/2, 2H9/2-->4I15/2, 2P3/2-->4I11/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 and 4S3/2-->4I13/2 transitions, respectively. Though incorporation of PbO and PbF2 both enhances fluorescence intensities however, PbF2 content has an important influence on upconversion luminescence emission. The incorporation of PbF2 enhances the red emission (658 nm) intensity by 1.5 times and the violet emission (410 nm) intensity by 2.0 times. A concentration dependence study of fluorescence reveals the rapid increase in the red (4F9/2-->4I15/2) emission intensity relative to the green (4S3/2-->4I15/2) emission with increase in the Er3+ ion concentration. This behaviour has been explained in terms of an energy transfer by relaxation between excited ions.     

Structural, optical, physical and electrical properties of V2O5.SrO.B2O3 glasses

The present work aims to study the structure and variation of optical band gap, density and dc electrical conductivity in vanadium strontium borate glasses. The glass systems xV2O5.(40-x)SrO.60B2O3 and xV2O5.(60-x)B2O3.40SrO with x varying from 0 to 20 mol% were prepared by normal melt quench technique. Structural studies were made by recording IR transmission spectra. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. The position of absorption edge and hence the value of the optical band gap was found to depend on the semiconducting glass composition. The absorption in these glasses is believed to be associated with indirect transitions. The origin of Urbach energy is associated with the phonon-assisted indirect transitions. The change in both density and molar volume was discussed in terms of the structural modifications that take place in the glass matrix on addition of V2O5. dc conductivity of the glass systems is also reported. The change of conductivity and activation energy with composition indicates that the conduction process varies from ionic to polaronic one.     

Luminescent properties of Tb3+ and Gd3+ ions doped aluminosilicate oxyfluoride glasses

Tb³⁺ and Gd³⁺ ions doped lithium–barium–aluminosilicate oxyfluoride glasses have been prepared. The transmission, emission and excitation spectra were measured. It has been found that those Tb³⁺-doped lithium–barium–aluminosilicate oxyfluoride glasses exhibit good UV-excited luminescence. The luminescence intensity of Tb³⁺ ion increases for those (Tb³⁺, Gd³⁺)-codoped glasses. Energy transfer process from Gd³⁺ ion to Tb³⁺ ion is indicated.     

The effect of Er3+ and Sm3+ on phase separation and crystallization in Na2O/K2O/BaF2/BaO/Al2O3/SiO2 glasses

Thermal annealing of Sm⁺³ or Er⁺³ doped Na₂O/K₂O/BaF₂/BaO/Al₂O₃/SiO₂ glasses led to the precipitation of nanocrystalline BaF₂. The mean crystallite sizes were in the range from 9 to 15 nm as shown by XRD line broadening. Whereas glasses without rare earth oxides showed crystallites homogenously dispersed in the amorphous matrix, those doped with 0.05 mol% ErF₃ or SmF₃ showed highly agglomerated crystals. The latter was due to droplet phase separation in the rare earth doped glasses as proved by transmission electron microscopy while in the undoped glasses phase separation did not occur. Furthermore, the size of the droplets depended on the BaO-concentration. Fluorescence emission spectra of a samarium doped sample showed higher intensities than in the glasses they were prepared from.     

Spectroscopic properties of Er3+, Yb3 + and Er3 + /Yb3+ doped metaphosphate glasses

The absorption and emission spectroscopies of Er3+ doped and Er3+/Yb3+ codoped Ca(PO3)2, Sr(PO3)2 and Ba(PO3)2 glasses have been studied. From the Judd-Ofelt intensity parameters, the spontaneous emission probabilities of some relevant transitions and the radiative lifetimes of several excited states of Er3+ have been calculated. The decay curves of the Er3+ emission at 1.5 microm have been measured at different temperatures. The data have been fitted using a stretched exponential function and the obtained experimental lifetimes have been compared with the calculated radiative lifetimes. The difference between the experimental and calculated lifetimes is attributed to the presence of traces of OH groups in the host glasses. The absolute OH content in some glasses has been determined from the infrared spectra. The emission spectra at 1.5 microm of the Er3+ ion in the codoped glasses have been measured at different temperatures. The integrated emission intensities decrease significantly on passing from room temperature to 13 K, suggesting a temperature dependence of the rate of the energy transfer process between Yb3+ and Er3+.     

Li2MnO3 content effects on thermal,structural, electrical and electrochemical properties of xLi2MnO3-(1-x)LiNi0.9Zn0.1O2 cathode materials

xLi₂MnO₃-(1-x)LiNi_0.9Zn_0.1O₂ (x = 0.1, 0.2 and 0.3) cathodes were prepared by two steps solid-state reaction method. Layered crystalline phases (space groups of C2/m for Li₂MnO₃ and R3m for LiNi_0.9Zn_0.1O₂) were detected in all cathodes. FTIR study also revealed the formation of the layered-type structures of all cathodes. The structural parameters were greatly influenced by the contents of Li₂MnO₃ in xLi₂MnO₃-(1-x)LiNi_0.9Zn_0.1O₂. The electrical conductivities were found in the range of 1.2 × 10^?6 to 2.7 × 10^?6 S/cm. The dielectric spectra revealed the interfacial polarization Maxwell–Wagner type dielectric dispersion existing in all samples. The cathodes delivered the discharge capacities of 149 (x = 0.1), 151 (x = 0.2) and 157 mAh/g (x = 0.3) with capacity retention between 94.6 and 96.8% when they were cycled from 3.0 to 4.5 V under 0.1C rate. The x = 0.3 cathode exhibited the highest cyclic performance (96.8%) after 10 cycles due to its lower cations disorder.     

Thermal properties and optical transition probabilities of Tm3 + doped TeO2-WO3 glass.

Glasses with the composition of (1 - x)TeO2 + (x)WO3, where x = 0.15, 0.25 and 0.3 were prepared and, their thermal and absorption measurements were carried out. Differential thermal analysis (DTA) curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while crystallization was not observed for the glasses containing a WO3 content of more than 15 mol%. All the glasses were found to be moisture-resistant. The absorption bands corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of the Tm3+ ion were observed in the optical absorption spectra. Integrated absorption cross-sections of each band except that of 3H5 level was found to vary with the glass composition. Judd-Ofelt analysis was carried out for the samples doped with 1.0 mol% Tm2O3. The omega2 parameter shows the strongest dependence on the host composition and it increases with the increasing WO3 amount. The value of omega4 increases rather slowly while the value of omega6 is practically independent of the composition. The strong dependence of the parameter omega2 indicates that this parameter is related to the structural change and the symmetry of the local environment of the Tm3+ ions in this glass.     

Synthesis and optical properties of Gd2O3:Pr3+ phosphor particles

Spherical-shaped Gd₂O₃:Pr³⁺ phosphor particles were prepared with different concentrations of Pr³⁺ using the urea homogeneous precipitation method. The resulting Gd₂O₃:Pr³⁺ phosphor particles were characterized by X-ray diffraction, field emission scanning electron microscope, and photoluminescence spectroscopy. The effects of the Pr³⁺ doping concentration on the luminescent properties of Gd₂O₃:Pr³⁺ phosphors were investigated. Photoluminescence measurements revealed the Gd₂O₃:1?% Pr³⁺ phosphor particles to have the strongest emission. The luminescence properties of Gd₂O₃:Pr³⁺ particles are strongly affected by the phosphor crystallinity and X-ray diffraction measurements confirmed that the crystallinity of Gd₂O₃ cubic structure could be enhanced by increasing the firing temperature. The luminescent Gd₂O₃:Pr³⁺ phosphor particles have potential applications in areas, such as optical display systems, lamps and etc.     

Open air annealing effect on the electrical and optical properties of tin doped ZnO nanostructure

Transparent conducting undoped and tin doped ZnO multilayer films were deposited by sol-gel method. Effect of open air annealing on different parameters like grain size, carrier density, band gap, resistivity, refractive index and extinction coefficient were investigated. Films were deposited on glass and silicon substrate by keeping doping concentration 4 at%. It was observed that tin doping reduces resistivity from 194.6 Ω cm to 3.11 Ω cm. Optical transmission spectra exhibit transmittance above 88% in visible range. Maximum carrier density of 11.9 × 10¹⁸ cm⁻³ and band gap of 3.24 eV was estimated at 375 °C. Scanning Electron Microscopy showed homogenous worm like morphology. Atomic force microscopy revealed pyramid shaped nanostructure of tin doped ZnO.     

Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y2O3)(0.2)-(Al2O3)x-(B2O3)(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 ≤ x ≤ 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly "aluminate-like" with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.     

Theoretical investigations on the defect structures and g factors for V4+ in 30PbO-5Bi2O3-(65-x)SiO2 glasses at different concentrations

For 3d¹ (V⁴⁺) impurity in 30PbO-5Bi₂O₃-(65-x)SiO₂ glass systems with different concentrations x of V2O5, the defect structures and gyromagnetic factors are theoretically investigated by using the perturbation formulas of g factors for a tetragonally compressed octahedral 3d¹ group. The concentration dependences of d-d transition band and g factors are suitably explained from the Fourier type concentration functions of the cubic crystal field parameter Dq, covalency factor N and relative tetragonal compression ratio ρ. The above concentration dependences of these quantities are suitably illustrated by the modifications of the local crystal field strength and electron cloud distribution with increasing x. The concentration variations of the electrical conductivity and dielectric relaxation are further analyzed from the stability of the systems in view of two competitive factors (increasing network polymerization and bulk stability at low concentrations and decreasing former SiO₂ and stability at high concentrations).     

Optical characterization of Sm3+ and Dy3+:ZnO-PbO-B2O3 glasses

Here, we present the results of the analysis of Sm(3+) or Dy(3+) (0.5 mol%) ions doped heavy metal oxide (HMO)-based zinc lead borate (ZLB) glasses. Optical measurements such as absorption, emission spectra, lifetimes, XRD, DSC profiles have been carried out. The emission spectrum of Sm(3+):ZLB has shown the emission transitions of (4)G(5/2)-->(6)H(5/2) (563 nm), (4)G(5/2)-->(6)H(7/2) (598 nm), (4)G(5/2)-->(6)H(9/2) (646 nm), (4)G(5/2)-->(6)H(11/2) (708 nm) with lambda(exc): 401 nm ((6)H(5/2)-->(4)F(7/2)). In the case of the Dy(3+):ZLB glass, emission transitions of (4)F(9/2)-->(6)H(15/2) (485 nm), (4)F(9/2)-->(6)H(13/2) (575 nm) and (4)F(9/2)-->(6)H(11/2) (664 nm) with lambda(exi): 447 nm ((6)H(15/2)-->(4)I(15/2)) have been identified. Energy level schemes relating to the emission mechanisms involved in Sm(3+) and Dy(3+) glasses have been given.