Structural investigations of copper doped B2O3-Bi2O3 glasses with high bismuth oxide content

Raman and infrared spectroscopy have been employed to investigate the 99.5%[xB₂O₃(1−x)Bi₂O₃]0.5%CuO glasses with different Bi/B nominal ratios (0.07?x?0.625) in order to obtain information about the competitive role of B₂O₃ and Bi₂O₃ in the formation of the glass network. The glass samples have been prepared by melting at 1100 °C and rapidly cooling at room temperature. In order to relax the structure, to improve the local order and to develop crystalline phases the glass samples were kept at 575 °C for 10 h. The influence of both Bi₂O₃ and CuO on the vitreous B₂O₃ network as well as the local order changes around bismuth and boron atoms in as prepared and heat treated samples was studied. Structural modifications occurring in heat treated samples compared to the untreated glasses have been observed.     

Structure and crystallization of potassium titanium phosphate glasses containing B2O3 and SiO2

Transparent glasses composition of which can be expressed by the formula: (100−x) · (K₂O · 2TiO₂ · P₂O₅) · x(K₂O · 2B₂O₃ · 7SiO₂), where x=5, 10, 15 and 20 mol% (KTP-xKBS), were obtained by melt quenching technique. The structure and crystallization behavior of these glasses have been examined by Fourier transform infrared spectroscopy, differential thermal analysis and X-ray diffraction. In spite of their nominal composition, the studied glasses exhibit a similar oxygen polyhedra distribution. However, significant differences were found in the trigonal BO₃ units amount. During DTA runs all the examined glasses devitrify in two steps. In the former, very small crystals of an unknown crystalline phase are produced. In KTP-5KBS and KTP-10KBS glasses anatase phase was also detected. Attempts were made in order to identify the unknown phase (UTP) for which a AB₃(XO₄)₂(OH)₆ Crandallite-type structure was proposed where the A, B and X sites were occupied by K, Ti and/or Al, and P, respectively. In the second devitrification step the crystallization of the KTiOPO₄ phase occurs while the UTP phase previously formed disappears. Isothermal heat treatments performed at temperature just above T_g have allowed one to obtain transparent crystal-glass nanocomposites, formed by crystalline nanostructure of the UTP phase uniformly dispersed in the amorphous matrix.     

Sintering process of glasses in the system Na2O-B2O3-SiO2

In this work, the sintering process of different glasses in the system Na₂O-B₂O₃-SiO₂ has been studied. The studied compositions are suitable for sealing the gas manifolds of molten carbonate fuel cells. Sealing glasses are usually applied on the surfaces to be sealed using powder glass mixed with an organic medium. The agglomerant elimination and the sintering of the glass powder take place during the thermal treatment. Three different particle sizes of glass powder and different sintering temperatures and times have been used to reveal the influence of the specific surface area and viscosity on sintering. The control of these parameters allows optimization of the sealing conditions of the glasses. Dense materials have been characterized as well as the sintering mechanism. Two processes take place during the thermal treatment: the sintering process and the quartz crystallisation. Both processes act in opposite directions on the glass densification. Crystallisation is the dominant process at long times and high temperatures. The viscous flow Scherer model has been adequately applied to the experimental data.     

Characterisation of ALCVD Al2O3-ZrO2 nanolaminates, link between electrical and structural properties

Al₂O₃ and ZrO₂ mixtures for gate dielectrics have been investigated as replacements for silicon dioxide aiming to reduce the gate leakage current and reliability in future CMOS devices. Al₂O₃ and ZrO₂ films were deposited by atomic layer chemical vapor deposition (ALCVD) on HF dipped silicon wafers. The growth behavior has been characterized structurally and electrically. ALCVD growth of ZrO₂ on a hydrogen terminated silicon surface yields films with deteriorated electrical properties due to the uncontrolled formation of interfacial oxide while decent interfaces are obtained in the case of Al₂O₃. Another concern with respect to reliability aspects is the relatively low crystallization temperature of amorphous high-k materials deposited by ALCVD. In order to maintain the amorphous structure at high temperatures needed for dopant activation in the source drain regions of CMOS devices, binary Al/Zr compounds and laminated stacks of thin Al₂O₃ and ZrO₂ films were deposited. X-ray diffraction and transmission electron microscope analysis show that the crystallization temperature can be increased dramatically by using a mixed oxide approach. Electrical characterization shows orders of leakage current reduction at 1.1-1.7 nm of equivalent oxide thickness. The permittivity of the deposited films is determined by combining quantum mechanically corrected capacitance voltage measurements with structural analysis by transmission electron microscope, X-ray reflectivity, Rutherford backscattering, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy. The k-values are discussed with respect to formation of interfacial oxide and possible silicate formation.     

Ablation and compaction of amorphous SiO2 irradiated with ArF excimer laser

The structure of amorphous SiO₂ exposed to ArF excimer laser irradiation was examined. Threshold fluence for causing ablation with a single pulse depended on sample preparation: more specifically, 1 J/cm² for thermally grown SiO₂ films on silicon and 2.5 J/cm² for bulk SiO₂. It was found that the bond angle of Si-O-Si was reduced by irradiation near the interface of thermally grown SiO₂ films. In contrast, evolution of the bond angle by irradiation was absent in both the bulk SiO₂ and SiO₂ film-near the top surface, even though the concentration of puckered four-membered rings deduced from Raman spectra dramatically increased. It is assumed that planar three-membered rings were generated in the SiO₂ thin layer near the interface, and puckered four-membered rings were generated in the bulk SiO₂. The concentration of both the Si³⁺ and Si²⁺ structure was increased at a fluence of 800 mJ/cm² with an increasing number of pulses, although generation of both was absent at higher fluence for a single pulse. The author proposes that the structure of SiO₂ is created by flash heating and quenching by pulse laser irradiation. Structural similarities were found between the irradiated SiO₂ and SiO₂ at high temperatures.     

Multinuclear NMR study of phosphosilicate gels derived from POCl3 and Si(OC2H5)4

Solid state ¹H, ²⁹Si and ³¹P MAS NMR have been used to investigate the microstructure of phosphosilicate gels prepared by a modified sol-gel method involving hydrolysis of silicon precursors in a solely aqueous environment at 50 °C. Gels with molar compositions 5, 10, 20 and 30 mol% P₂O₅ in P₂O₅-SiO₂ were studied. After drying to 400 °C the gels have very similar structures formed by a siloxane framework containing silanol groups and trapped molecules of orthophosphoric acid together with a very small amount, of pyrophosphoric acid. Unlike the gel samples previously synthesized by the hydrolysis of the silicon precursor in alcoholic solution at room temperature, the co-polymerization of phosphorus and silicon is much reduced. Although co-polymerization increases with phosphorus content, it still represents less than 50% of the phosphorus in the 30 mol% P₂O₅ gel. Furthermore there is no evidence for six-coordinated silicon in the glassy matrix.     

Sol-gel preparation and optical properties of SiO2-Ta2O5 glass

Tantalum-doped silica glass was fabricated by the sol-gel process in order to obtain a glass with a high refractive index for optical use. A crack-free, clear glass rod was successfully prepared from a low-density gel and used as the core material for fabricating optical fibers. Transmission loss in the fabricated fibers was high, in the range of 10³-10⁴ dB/km, which may be caused by coloration due to the multivalency of tantalum; however, the loss was reduced by nearly one order of magnitude by heat treatment at 800 °C, that is, to 75 dB/km at a wavelength of 0.8 μm.     

The effect of alumina on the Sn/Sn redox equilibrium and the incorporation of tin in Na2O/Al2O3/SiO2 melts

Glasses with the basic compositions 10Na₂O · 10CaO · xAl₂O₃ · (80 − x)SiO₂ (x=0, 5, 15, 25) and 16Na₂O · 10CaO · xAl₂O₃ · (74 − x)SiO₂ (x=0, 5, 10, 15, 20) doped with 0.25-0.5 mol% SnO₂ were studied using square-wave-voltammetry at temperatures in the range from 1000 to 1600 °C. The voltammograms exhibit a maximum which increases linearly with increasing temperature. With increasing alumina concentration and decreasing Na₂O concentration the peak potentials get more negative. Mössbauer spectra showed two signals attributed to Sn²⁺ and Sn⁴⁺. Increasing alumina concentrations did not affect the isomer shift of Sn²⁺; however, they led to increasing quadrupole splitting, while in the case of Sn⁴⁺ both isomer shift and quadrupole splitting increased. A structural model is proposed which explains the effect of the composition on both the peak potentials and the Mössbauer parameters.     

Molecular dynamics simulation of La2O3-Na2O-SiO2 glasses. II. The clustering of La cations

Clustering of high-field strength rare-earth ions in silicate glasses has been experimentally observed for a wide range of concentrations. Clustering has also been observed by molecular dynamics (MD) computer simulations over a range 1-10 mol% in soda silicate glasses. Although there have been numerous experimental studies, atomic-level details of the mechanisms that lead to clustering remain unclear. Coupling experiment with MD simulations is essential to uncovering the factors that lead to clustering. In this work, MD computer simulations are used to verify that clustering found in previous MD simulations is not an artifact of the simulation method. This work also provides clues as to the mechanism of atomic-level clustering.     

Effect of Y2O3 addition on the phase transition and growth of YSZ nanocrystallites prepared by a sol-gel process

The effect of Y₂O₃ addition on the phase transition and growth of yttria-stabilized zirconia (YSZ) nanocrystallites prepared by a sol-gel process with various mixtures of ZrOCl₂ · 8H₂O and Y(NO₃)₃ · 6H₂O ethanol-water solutions at low temperatures has been studied. DTA/TGA, XRD, SEM, TEM and ED have been utilized to characterize the YSZ nanocrystallites. The crystallization temperature of 3YSZ, in which Y₂O₃/(Y₂O₃ + ZrO₂) = 0.03, gel powders estimated by DTA/TG is about 427 °C. When 3YSZ and 5YSZ gels are calcined at 500-700 °C, their crystal structures as composed of coexisting tetragonal and monoclinic ZrO₂, and tetragonal phase decreases with calcination temperature increasing from 500 to 700 °C. Pure cubic ZrO₂ is obtained when added Y₂O₃ is greater than 8 mol%. A nanocrystallite size distribution between 10 and 20 nm is obtained in TEM observations.     

Cobalt ortho- and para-substituted tetraphenylporphyrins inserted in SiO2 gels

The sol-gel method, generally, allows the trapping of important organic and biological systems in inorganic networks. Free and metallic porphyrins feature a wide range of important electrical, optical, and catalytic properties. To fix them in gels it is necessary to substitute an appropriate reactive group in the periphery of the macrocycle, which thus becomes more soluble in water or alcohols. The substituents more frequently employed have been -SO₃⁻, -Na⁺, -COOH and pyridinium salts. We have tried to increase the number, type, and spatial position of such substituents, to evaluate their influence in the quality and properties of the final materials. In this work we report the results obtained with the Co(II) complexes of the meso-5,10,15,20-tetraphenylporphyrin macrocycle, in which the amino, -NH₂(basic) or hydroxyl, -OH (acid) groups have been placed in the ortho- and para-positions of the phenyl groups. The insertion of cobalt porphyrins was made possible by the addition of small quantities of pyridine, methanol or dimethylformamide (DMF). Maxima in the transparency and strength of the materials were obtained with the para-amino substituted porphyrin, when methanol and pyridine were employed as the solvent media. Our results reveals that methanol has no influence on the morphology of the silica network, but DMF changes it drastically. The procedure here described has been successfully extended to trap other free and metallic porphyrinic systems.     

Formation of oxygen-deficient type structural defects and state of ions in SiO2 glasses implanted with transition metal ions

The properties and concentrations of oxygen-deficient type structural defects in type III SiO₂ glasses implanted with Ti⁺, Cr⁺, Mn⁺, Fe⁺, or Cu⁺ to doses from 0.5×10¹⁶ to 6×100¹⁶ ions/cm² at an energy of 160 keV have been measured by using vacuum UV and EPR spectroscopies. An intense absorption band centered around 7.5 eV is observed in all the samples except for Cu-implanted ones and is attributed primarily to Si---Si homo-bonds with the bond distance close to that of the Si₂H₆ molecule. The homo-bond and implanted ion concentrations are of the same order of magnitude in the implanted layers. An E′ type center associated with the homo-bond is observed in all the samples except for Cu-implanted ones. Anomalous behaviors of the Cu-implanted samples are attributed to the formation of Cu-colloids. An enhanced formation of metallic particles or colloids is suggested for the samples implanted with Cr, Mn or Fe to doses higher than 3×10¹⁶ ions/cm².     

Structural and physical properties of a novel TeO2-BaO-SrO-Ta2O5 glass system for photonic device applications

A detailed study on a novel TeO₂-BaO-SrO-Ta₂O₅ glass system developed for photonic device applications is reported in this paper. The glass transition and crystallization temperatures could be selected by varying the Ta₂O₅ content in this glass system. This glass system is found to have good thermal stability among tellurite glasses. Raman spectroscopy has been used as a tool to analyze the structural details of this technologically important glass system. In addition to the TeO₄ trigonal bipyramid and TeO₃ trigonal pyramid structural units, glasses in this system revealed the presence of an additional Raman band attributed to TaO₆ octahedra. The Raman bandwidth of the present glasses are broader compared to the conventional tellurite glasses by 35%. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated. Unlike the other tellurite glasses, even at higher modifier concentrations the TeO₄ structural units dominate in the glass network compared to TeO₃ trigonal pyramids. The ratio of TeO₄/TeO₃ structural units was discussed for different series of glass compositions.     

Preparation and characterization of transparent Eu doped Y2O3 aerogel monoliths, for application in luminescence

This paper focuses on a new sol-gel preparation method of Eu doped Y₂O₃ aerogels, for application in luminescence and their characterization. The preparation method is based on a sol-gel technique using metal salts, by controlling the hydrolysis of these precursors with an epoxide. The monoliths prepared in this manner are transparent in the visible radiation domain. They have a mesoporous texture, a specific surface area of ≈350 to 400 m² g⁻¹ and they are X-ray amorphous. The gel network could be clearly observed by Transmission Electron Microscopy and showed the presence of localized poorly crystalline nanodomains, with some Eu segregation. A first evaluation of the luminescence which they develop during crystallization, has been carried out as a function of the heat treatment schedule.     

Crystallization behavior and microstructure of powdered and bulk ZnO-Al2O3-SiO2 glass-ceramics

The crystallization behavior of glass with the composition: 55.6 mol% SiO₂, 22.8 mol% Al₂O₃, 17.7 mol% ZnO and 3.84 mol% of TiO₂ as nucleating agent and with different particle sizes has been studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tranmission electron microscopy (TEM). In glass powders two crystalline phases: zinc-aluminosilicate s.s. with high-quartz structure, Zn_x/2Al_xSi_3−xO₆, (x varies dependent on heat-treatment temperature) and gahnite are formed. The ratio of these phases depends on particle sizes. In bulk glass, however, gahnite is the sole crystalline phase. The composition of initially formed zinc-aluminosilicate s.s. was determined by Rietveld refinement of XRD patterns to be Zn_0.69Al_1.38Si_1.62O₆. With temperature increase, the amount of zinc-aluminosilicate s.s decreased with simultaneous reduce of zinc and aluminum incorporated in the structure. Eventually at 1423 K almost pure high-quartz structure was formed. The activation energies of zinc-aluminosilicate s.s. and gahnite crystallization were determined by non-isothermal method to be 510 ± 18 and 344 ± 17 kJ mol⁻¹, respectively. The latter value matches well with those cited in literature for crystal growth of gahnite in similar glasses. That is attributed to the fact that the high-quartz structure acts as a precursor for gahnite crystallization.     

Optical Properties of Bi2O3-TeO2-B2O3 Glasses

Glasses of the Bi₂O₃-TeO₂-B₂O₃ ternary system were developed and their linear and nonlinear optical properties were investigated. The absorption edges of these glasses were found to be 367-384 nm with a good transmittance in visible wavelength, although they exhibit the refractive indices as high as 1.98-2.12 at 633 nm. The absorption edges are quite steep and they are analyzed by the Urbach theory. The obtained Urbach energies of these glasses are 73-79 meV which are comparable to silica glasses. The high refractive index and its glass composition dependency are discussed according to the basics of the electronic polarizability and optical basicity. The high third order nonlinear susceptibility χ⁽³⁾ = 2.0 × 10^− 12 esu at 800 nm was also obtained in the 36Bi₂O₃-18TeO₂-46B₂O₃ glass.     

Refractive index-structure correlations in Na2O-Al2O3-SiO2 glasses

The current structural models have been used to analyse the refractive index data of Na₂O-Al₂O₃-SiO₂ glasses (Al₂O₃/Na₂O?1). The SiO₂ content is the sole factor that controls the refractive index. Values could be obtained for the factors with which each structural unit contributes in the refractive index. The content of Al₂O₃ or Na₂O has no effect on the refractive index. The factors (differential refraction) are constant and do not change with composition. They have the same values for Na₂O-SiO₂ glasses. The differential refraction of a structural unit increases linearly with increasing the number of non-bridging oxygen ions. The difference of the contribution to the refractive index from a silicate unit to the next equals to a half of that for AlO₄ tetrahedron. The effect could be attributed to the change in both the concentration and differential refraction of structural units. The obtained factors for the structural units are useful in calculating the refractive index with a high degree of accuracy.