Structural investigations of the xTeO2-(1−x)GeO2 (x=0, 0.2, 0.4, 0.6, 0.8 and 1) tellurite glasses: A composition dependent Raman spectroscopic study

Raman spectra of xTeO₂-(1−x)GeO₂ (x=0, 0.2, 0.4, 0.6, 0.8 and 1) germanium tellurite glasses were measured and analyzed in an effort to follow the structural changes caused by mixing two typical glass formers. Systematic Raman intensity measurements have been performed in an effort to elucidate the composition induced structural changes and a possible mechanism accounting for these changes was proposed. The network structure of the glass is characterized by TeO₄ trigonal bipyramid mixed with TeO₃ trigonal pyramid units, while GeO₄ tetrahedral units are also present. Changing the GeO₂ content results in the conversion of the TeO₄ units to TeO₃ units with a neutral doubly bridged oxygen atom, while the existence of charged terminal oxygen atoms is questionable. The measured relative Raman intensities are semi-quantitatively correlated to the transformation of the TeO₄ trigonal bipyramid to TeO₃ trigonal pyramids.     

Spectroscopic studies on Li2O–MgO–Bi2O3–B2O3 glasses

MgO-Li₂O-Bi₂O₃-B₂O₃ glasses were prepared by melt quench technique and analyzed with the help of refractive index, optical, IR, and Raman spectroscopy studies. The present glasses exhibited the mixed modifier effect (MME) through refractive index change non-linearly. The variation in the indirect optical band gap and band tailing in MgO content have been discussed with the glass structure. Based on the obtained values of α_o2-, optical basicity, and interaction parameters, the present glasses were termed as very semi covalent acidic oxide glasses. Raman and Infrared spectra reveal that these glasses are built up of BO₃, BO₄ units of B₂O₃ and octahedral [BiO₆], pyramidal [BiO₃] units of Bi₂O₃ were observed.     

Structure of zinc-borate low-melting glasses derived from IR spectroscopy data

The IR spectra of glasses of the ZnO—SrO—B₂O₃ system with constant additions of PbO, Al₂O₃, and Li₂O (20 mol. % in sum) were studied. It is established that on replacement of B₂O₃ by ZnO, the structure of the glasses is characterized by the presence of groupings with the bridge bonds B^III— O—B^III, B^III—O—B^IV, B^IV—O—B^IV and end groups B^III— O⁻; ZnO practically exerts no influence on the coordination transition [BO₃] → [BO₄]. At a high content of ZnO, zinc ions are present in both a six-and a four-coordinated state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 778–781, November–December, 2005.     

Spectroscopic analysis and magnetic susceptibility of CuO-TeO2-V2O5 glasses

This article reports on the structure of the glassy system xCuO-65TeO₂-(35−x)V₂O₅, 5≤x≤10 mol% which was studied using infrared (IR) and Raman spectroscopy methods as well as magnetic susceptibility measurements. IR and Raman spectroscopy analysis reveals the presence of four main absorption bands attributed to [TeO₃], [TeO₄], [VO₄], and [VO₅] structure units. It suggests that Cu²⁺ ions occupy the available open spaces of the Te-O network without straining the bonds too much. Increasing the concentration of Cu²⁺ ions beyond 5 mol% results in the modification of the glass by straining and locally distorting the surrounding of the Te-O network. The magnetic susceptibility of these materials was investigated in the temperature range of 5-200 K revealing the paramagnetic behavior described by the Curie-Weiss law and indicating the presence of weak antiferromagnetic exchange interactions between Cu ions. The magnetic entropy change of the glasses was determined based on the temperature and magnetic field dependence of magnetization.     

GeO2含量对掺铒锗碲酸盐玻璃物性和光谱特性的影响

本文研究了x GeO₂-(70-x)TeO₂-5K₂O-5Na₂O-10Nb₂O₅-10ZnO-0.2Er₂O₃(x=0,10, 25, 50, 70(摩尔百分数))玻璃的物性和光谱特性，讨论GeO₂含量对锗碲酸盐玻璃物性和光谱特性的影响.研究发现：GeO₂的加入提高了碲酸盐玻璃热稳定性， 关键词： 锗碲酸盐玻璃 玻璃热稳定性 荧光     

Optical,physical and structural studies of boro-zinc tellurite glasses

To investigate the modification effect of the modifier ZnO on boro-tellurite glass, a series of glasses with compositions 50B₂O₃–(50?x)ZnO–xTeO₂ have been prepared by conventional melt quenching technique. Amorphous nature of the samples was confirmed through X-ray diffraction technique. Optical absorption and IR structural studies are carried out on the glass system. The optical absorption studies revealed that the cutoff wavelength increases while optical band gap (E_opt) and Urbach energy decreases with an increase of ZnO content. Refractive index evaluated from E_opt was found to increase with an increase of ZnO content. The compositional dependence of different physical parameters such as density, molar volume, oxygen packing density, optical basicity, have been analyzed and discussed. The IR studies showed that the structure of glass consists of TeO₄, TeO₃/TeO₃₊₁, BO₃, BO₄ and ZnO₄ units.     

Raman characterizations and structural properties of the binary TeO2?WO3, TeO2?CdF2 and ternary TeO2?CdF2?WO3 glasses

The Raman spectroscopy technique was used to characterize the microstructure and the crystallization properties of the as‐cast and heat‐treated binary TeO₂ WO₃, TeO₂ CdF₂ and ternary TeO₂ CdF₂ WO₃ glasses and glass ceramics. The results were compared with those obtained by using the X‐ray diffraction technique. The effect of the WO₃ and CdF₂ contents on the TeO₂ glass network and the intensity ratios of the deconvoluted Raman peaks were determined. The shifts in the Raman band wavenumbers and the intensity values for each band were investigated. The Raman results indicated that the glasses were mainly formed by the [TeO₄] and [TeO₃] units. The [TeO₄] units convert to [TeO₃] units with the addition of WO₃ and CdF₂ into tellurite glasses. All the crystalline phases such as α‐TeO₂, δ‐TeO₂ and γ‐TeO₂ existing in the TeO₂ WO₃, TeO₂ CdF₂ and TeO₂‐ WO₃ CdF₂ glasses were determined. The transformation of the metastable γ‐TeO₂ phase into stable α‐TeO₂ was observed for the (1 − x)TeO₂ xWO₃ (where x = 0.15, 0.20, 0.25), 0.90Te₂ 0.10CdF₂, the 0.85TeO₂ 0.10CdF₂ 0.05WO₃ and 0.80TeO₂ 0.10CdF₂ 0.10WO₃ glasses, and the transformation of the metastable δ‐TeO₂ phase into the stable α‐TeO₂ was also observed for the TeO₂ CdF₂ WO₃ glass system. In addition, an unidentified phase formation, labeled ε, was determined. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural studies of boron and tellurium coordination in zinc borophosphate glasses by 11B MAS NMR and Raman spectroscopy

Zinc borophosphate glasses doped with TeO₂ with different B₂O₃/P₂O₅ ratio were prepared, their basic properties were determined and their structure was studied by ¹¹B MAS NMR and Raman spectroscopies. Structural studies were devoted to the investigation of changes in boron coordination in the dependence on changes in TeO₂ content and in B₂O₃/P₂O₅ ratio in the borophosphate glasses. A special attention was devoted to the formation of mixed structural units B(OP)_4?n(OTe)_n in the studied borophosphate glasses, where by the deconvolution of ¹¹B MAS NMR spectra quantitative data on the number of BO₃ and B(OP)_4?n(OTe)_n mixed structural units were obtained. Raman spectra showed shortening of phosphate chains both with increasing TeO₂ and B₂O₃ content. Raman spectra also showed that with the replacement of P₂O₅ by B₂O₃ in the studied glasses TeO₄ units are replaced by TeO₃ units as the number of oxygen atoms in the glass decreases when the B₂O₃/P₂O₅ ratio increases.     

Novel photosensitive properties of gadolinium–lead germanate glasses

Glasses of the system xGd₂O₃ · (100 ? x)[7GeO₂ · 3PbO] with 0 ≤ x ≤ 40 mol% were prepared using the melt quenching method. Lead germanate glasses are particularly interesting in the context of the germanate anomaly. In this paper, we investigate changes in the coordination number of germanium in gadolinium–lead germanate glasses using molar volume analysis, density measurements, FTIR and UV–VIS spectroscopy, and density functional theory (DFT). Despite some inconsistencies, the coordination change model remains the currently accepted model for the anomalous behaviour of lead germanate glasses. Based on these experimental results, we propose the following mechanism for the germanate anomaly. (i) The low thermodynamic stability of the [GeO₆] structural unit and the occupation of interstices of larger dimensions (the six-coordinated interstices of the [PbO₆] structural units) in the lead germanate network yield [GeO₅] structural units with higher thermodynamic stability and larger ionic radii. (ii) Not linked to the terminal oxygens of the [GeO₅] structural units and with the formation of smaller network cavities of the lead germanate glass, links are required with [GeO₄] tetrahedra for stabilization, generating the formation of three-membered rings of [GeO₄] tetrahedral structural units.     

Effect of B2O3 on the structure and properties of tungsten–tellurite glasses

The elastic properties and Debye temperatures of xB₂O₃–70TeO₂–(30–x)WO₃, (0 ≤ x ≤ 30 mol%) glasses have been investigated using sound velocity measurements at 4 MHz. Ultrasonic and thermal parameters, combined with the results of IR spectroscopic analyses, were employed to explore the effect of B₂O₃ on the structure of tungsten–tellurite glasses. According to IR analysis, there is competition between WO₆ and TeO₄ units to form BO₄ units, and the vibrations of the tellurite structural units are shifted towards lower wavenumbers on the formation of non-bridging oxygens. It is assumed that B₂O₃ acts as a modifier by decreasing the glass-transition temperature T _g and increasing both the thermal stability and glass formation range of the tellurite glasses. The change in density and molar volume with B₂O₃ content reveals that the borate units are less dense than the tellurite structural units. The observed compositional dependence of elastic moduli is interpreted in terms of the effect of B₂O₃ on the coordination number of the tellurite units. A good correlation was observed between experimentally determined elastic moduli and those computed with the Makishima–Mackenzie model.     

Theoretical investigations of the spin Hamiltonian parameters and local tetragonal distortions for Cu2+ in crystalline and amorphous TeO2 and GeO2

The spin Hamiltonian parameters (i.e., anisotropic g factors and hyperfine structure constants) and local tetragonal distortions for Cu²⁺ in crystalline and amorphous TeO₂ and GeO₂ are theoretically investigated using the high-order perturbation formulas of these parameters for a tetragonally elongated octahedral 3d⁹ cluster. The impurity Cu²⁺ occupying the octahedral sites are found to experience the relative tetragonal elongation ratios of about 11.4% and 9.5% for crystalline TeO₂ and GeO₂ and 10.8% and 6.6% for amorphous TeO₂ and GeO₂, respectively, along the C₄ axis due to the Jahn–Teller effect. This reveals the larger tetragonal elongation distortions for the Cu²⁺ centres in crystalline than amorphous systems (especially TeO₂). The theoretical spin Hamiltonian parameters show good agreement with the experimental data. The results are discussed.     

LiF-LiCl-B2O3系统非晶态快离子导体结构的研究

本文通过对¹¹B核磁共振(¹¹B-NMR)、红外光谱等实验方法,研究了LiF-LiCl-B₂O₃三元系统玻璃的结构和离子导电性,着重于F^-离子在玻璃网络中所起的作用,以及F^-,Cl^-和Li⁺离子对导电率的影响。LiF-LiCl-B₂O₃三元系统玻璃,随LiF含量的增加,B由三角体向四面体变化,从而F^-离子进入网络,使玻璃结构由[B₂O₃]三角体层状结构向三维空间延展,形成了含有[BO₃F]基团的三维空间网络,Cl^-离子以游离的离子存在于网络中,起着松散网络的作用,对提高电导率有利,而Li⁺离子作为传导离子,对电导率的贡献是主要的。本系统玻璃的电导率是随LiF,LiCl含量的增加而增大,在300℃时测得电导率σ=6.12×10^-4Ω^-1·cm^-1。 关键词：     

Spectroscopic Properties of Er3+/Yb3+-codoped PbO–Bi2O3–Ga2O3–GeO2 Glasses

We investigate the spectroscopic properties of the 1.5-μm emission from the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions in PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses for applications in broadband fiber amplifiers. The measured emission peak locates at 1,532 nm with a full width at half-maximum of ∼45 nm. The glasses exhibit a large stimulated emission cross-section of 0.89 × 10⁻²⁰ cm² and a large product of 40.0. Infrared-to-green upconversion occurs simultaneously upon excitation of the 1.5-μm emission with a commercially available 980 nm laser diode. The green-upconversion intensity has a quadratic dependence on incident pump laser power, indicating a two-photon process. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the ²H_11/2 of Er³⁺. The results indicate the possibility towards the development of lead–bismuth–gallate–germanate based glasses as photonics devices.     

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.     

Synthesis and structural investigations on TeO2-PbF2-CdF2 glasses and transparent glass-ceramics

New glasses have been prepared in the oxifluoride mixed system TeO₂-PbF₂-CdF₂. Starting from pure TeO₂ the addition of the fluorides leads to a decrease in the glasses characteristic temperatures. Also from Raman scattering results a structural evolution was observed where the number of structural units described as [TeO₃] trigonal pyramids and [TeO₃₊₁] polyhedra increases at the expense of the [TeO₄] trigonal bipyramids supposed to exist in the TeO₂ rich samples. Transparent glass ceramics were obtained from the glass with composition 80TeO₂-10PbF₂-10CdF₂ (mol%) with the PbTe₃O₇ crystalline phase being identified by X-ray diffraction and EXAFS measurements performed at the Te K, Cd K and Pb L_III edges. Also from Exafs measurements it is proposed that cadmium ions are preferentially surrounded by oxygen atoms although they were in a fluoride anion environment in the starting material.     

EPR and Optical Studies of Mo<Superscript>5+</Superscript> Ions in Lithium Molybdoborate Glasses

Electron paramagnetic resonance (EPR) and optical absorption studies of Li₂O–MoO₃–B₂O₃ with varying concentrations of Li₂O, MoO₃ and B₂O₃ have been carried out at room temperature. Two series of glasses, one with constant MoO₃ (CM) and another with constant borate (CB), have been investigated. Characteristic EPR spectra of Mo⁵⁺ have been observed centered around g ≅ 2.00, which are attributed to Mo⁵⁺ ion in an octahedral coordination sphere with an axial distortion. The spectra also show strong dependence on the concentration of Li₂O and B₂O₃. Spin concentrations (N) and magnetic susceptibilities (χ) have been calculated. In the CM series, the N values decrease with increasing Li₂O content up to 30 mol%, while in the CB series variation of N is found to increase initially up to 20 mol%, and with further increase in the Li₂O content the N values tend to decrease. The variation of magnetic susceptibilities is almost similar to that observed with the variation of N. From the optical absorption spectra, an absorption edge (α) has been evaluated. In the CM series, the values of α show a blueshift. On the other hand, in the CB series a redshift is observed. The observed variations in spectral parameters are explained by considering the molybdoborate network. Addition of Li₂O to the CM and CB series results in modification of [MoO_6/2]⁰ → [MoOO_5/2]⁻ and [BO_3/2]⁰ → [BO_4/2]⁻ → [BOO_2/2]⁻ groups, respectively, leading to creation of nonbridging oxygens. The optical basicity of the glasses has been evaluated in both the CM and the CB glasses. The optical basicity can be used to classify the covalent-to-ionic ratios of the glass, since an increasing optical basicity indicates decreasing covalency. It is observed that the covalency between Mo⁵⁺ ions and oxygen ligands increases in the CB series, whereas in the CM series the covalency between Mo⁵⁺ ions and oxygen ligands decreases. Authors' address: R. P. Sreekanth Chakradhar, Glass Technology Laboratory, Central Glass and Ceramic Research Institute, Kolkata 700032, India     

Vapor–liquid–solid growth and narrow-band ultraviolet photoluminescence of well-aligned GeO2 nanowire arrays with controllable aspect ratios

GeO₂ nanowire arrays have been fabricated by thermal evaporation of Ge powder in air via a vapor–liquid–solid mechanism with Au as a catalyst. The GeO₂ nanowires are single crystalline with a hexagonal structure and have a controllable aspect ratio in the range of 23–167. The controllable synthesis of GeO₂ nanowire arrays with different aspect ratios was achieved by adjusting the heating temperature and time. Photoluminescence spectra of the GeO₂ nanowire arrays were measured at room temperature, and two ultraviolet emission peaks at 347 and 364 nm are observed for the first time, which indicates that the GeO₂ nanowire arrays may have potential applications in nanoscale photonic and electronic devices. Moreover, this vapor–liquid–solid growth process may be employed for synthesis of the highly oriented nanowire arrays of other oxides, and provides opportunities for both fundamental research and technological applications.     

Structural and optical properties of WO3-ZnO-PbO-B2O3 glasses

Glass samples of compositions 20PbO-80B₂O₃ and xWO₃—(20−x) ZnO-20PbO-60B₂O₃ with x varying from 0% to 10% mole fraction are prepared by the melt quench technique. Decrease in the band gap from 2.86 to 2.16 eV for ZnO-PbO-B₂O₃ glasses with an increase in the WO₃ content has been observed and discussed. The FTIR spectral studies have pointed out the conversion of structural units of BO₃ to BO₄ and WO₄ to WO₆ with the presence of W-O-W vibration of tungsten and incorporation of ZnO₄ structural units of zinc in these glasses. The increase in density from 2.75 to 4.03 gcm⁻³ for ZnO-PbO-B₂O₃ glasses is observed with an increase in WO₃ content. Due to the formation of WO₆, WO₄ and BO₄ units, changes in the atomic structure with WO₃ composition are observed and discussed.     

Spectral-luminescent investigations of glasses and glass-ceramic materials in Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Glasses of 2Bi₂O₃-3GeO₂-xFe₂O₃ composition, where x = 0–1.5, are obtained under oxidizing and reducing conditions. Glass-ceramic materials are produced by the thermal treatment of the glasses, the properties of which, as well as those of the original glasses, are studied by the methods of X-ray phase analysis and optical and luminescent spectroscopy. It is found that the Fe³⁺/Fe²⁺ ion ratio in the samples changes depending on the synthesis conditions of the original glasses and crystallization process.     

Facile liquid phase deposition of thick reflective GeO2 film for hollow waveguide delivery of CO2 laser radiation

A new idea of using LPD (liquid phase deposition) to prepare a GeO₂ thick reflective film for hollow waveguide delivery of CO₂ laser radiation was investigated in this work. The LPD process was achieved by designedly adding acid to GeO₂–aqueous ammonia. The addition of acid could induce the transformation of germanate ions into GeO₂ solutes, leading to the deposition of a GeO₂ ceramic film when the concentration of GeO₂ solute is higher than its saturation solubility. It was found that the highest film growth rate occurred at a pH value of 3, while a film with low surface roughness and good adhesion to the substrate was produced at a pH value of 2 and the film could be converted to a smooth, compact hexagonal GeO₂ film by heat treatment at 1120 °C for 30 min. Two abnormal dispersion bands within 7.6–9 μm and 9.6–11.2 μm were mainly caused by the silica glass substrate and the GeO₂ film, respectively. The film was thick enough to achieve the total reflectance of the CO₂ laser radiation. The use of this GeO₂ film in a hollow waveguide structure for CO₂ laser radiation delivery is discussed based on the transmission loss and the feasibility of the deposition of the GeO₂ film inside silica capillary tubes. The results show that the hollow waveguides with low transmission loss are most likely fabricated at a low cost using the LPD-derived GeO₂ reflective film. PACS 78.20.-e; 78.66.-w; 42.70.-a; 78.20.Ci; 78.40.-q