Raman spectroscopic study on the structure of ZnCl2---ZnX2 and ZnCl2---KX (X = Br, I) glasses

Raman spectra have been measured for ZnCl₂---ZnX₂ and ZnCl₂---KX (X = Br, I) glasses to investigate the structure of the glasses with varying composition. The assignment of each band was made, and the change of the spectra with composition was explained in terms of the bridging and non-bridging states of halide ions and the change of the tetrahedral units, ZnX_nCl_4−n²⁻ (n = 0–4), formed in the glasses. As the content of ZnX₂ in ZnCl₂---ZnX₂ glasses increases (20 → 80 mol%), the peak frequency of the Zn---Cl stretching mode increases (238 → 248 cm⁻¹ in X = I glasses, 238 → 259 cm⁻¹ in X = Br glasses) while the Zn---I and Zn---Br stretching frequencies decrease (173 → 120 cm⁻¹ for Zn---I, 196 → 157 cm⁻¹ for Zn---Br). The decrease of the Zn---I and Zn---Br band frequencies was attributed to the increase of the number n of the ZnX_nCl_4−n²⁻ tetrahedra. The increase of the Zn---Cl frequency suggests the existence of the bonding state of Cl⁻ ions which is intermediate between the bridging and the non-bridging states. In ZnCl₂---KX glasses, the Zn---Cl_non-bridging band at about 300 cm⁻¹ was observed in addition to the bands observed in ZnCl₂---ZnX₂ glasses. The addition of KX produces non-bridging anions while the tetrahedral units, ZnX_nCl_4−n²⁻ are also formed.     

A comparison between the Raman modes of the tetrahedral network in amorphous and layered crystalline GeSe2

The characteristic A₁ peak at 199 cm⁻¹ in the Raman spectrum of amorphous GeSe₂ were compared with the peaks at 211 and 216 cm⁻¹ in the spectrum of crystalline GeSe₂. It was proved that the crystalline 216 cm⁻¹ peak is an intrinsic mode which is enhanced by the bulk exciton transition. From a model calculation using a valence force field and bond polarizability, the 211 cm⁻¹ peak was assigned to in-phase breathing vibrations extended along the GeSe₄ tetrahedral chain structure, while the 216 cm⁻¹ peak was attributed to in-phase breathing vibrations quasi-localized at the GeSe₄ edge-sharing tetrahedra. The phonon density of states in the crystal has a doublet peak similar to the amorphous Raman spectrum. A correspondence between the amorphous and the crystalline Raman spectra was proposed.     

Raman spectrum studies of the glasses in the system Na2O---Al2O3---P2O5

Raman spectra of ternary sodium aluminosphosphate glasses indicate that for glasses with Al₂O₃/P₂O₅<0.63, the glass network is mainly built up of (PO₃)_n^n- chains and rings or different kinds of phosphate groups and AlO₄ tetrahedra; for glasses with Al₂O₃/P₂O₅>0.63, the glass network is mainly built up of AlPO₄ groups.     

Electronic traps in mixed Si1−xGexO2 films

Thermally stimulated luminescence (TSL) and infrared (IR) spectroscopy were measured in plasma grown Si_1−xGe_xO₂ (x=0, 0.08, 0.15, 0.25, 0.5) with different thicknesses (12–40 nm). A comparison with the TSL properties of thermally grown SiO₂ and GeO₂ was also performed. A main IR absorption structure was detected, due to the superposition of the peaks related to the asymmetric O stretching modes of (i) Si–O–Si (at ≈1060 cm⁻¹) and (ii) Si–O–Ge (at 1001 cm⁻¹). Another peak at ≈860 cm⁻¹ was observed only for Ge concentrations, x>0.15, corresponding to the asymmetric O stretching mode in Ge–O–Ge bonds. A TSL peak was observed at 70°C, and a smaller structure at around 200°C. The 70°C peak was more intense in all Ge rich layers than in plasma grown SiO₂. Based on the thickness dependence of the signal intensity we propose that at Ge concentrations 0.25x0.5 TSL active defects are localised at interfacial regions (oxide/semiconductor, Ge poor/Ge rich internal interface, oxide external surface/atmosphere). Based on similarities between TSL glow curves in plasma grown Si_1−xGe_xO₂, thermally grown GeO₂ and SiO₂ we propose that oxygen vacancy related defects are trapping states in Si_1−xGe_xO₂ and GeO₂.     

Structural analysis of CaSiO3 glass by X-ray diffraction and Raman spectroscopy

The short-range structure of CaSiO₃ glass was studied by a combination of radial distribution analysis with an intensity comparison method on the basis of X-ray diffraction data. Three main peaks appeared at 1.64, 2.43 and 3.64 Å in the radial distribution function curve. The Raman bands were observed at 367, 642, 878 and 972 cm⁻¹ and the Raman spectrum was found to be similar to that observed in pyroxenes: single chains consisting of SiO₄ tetrahedra are linked by calcium ions laterally. The calcium ion is surrounded by six oxygen atoms at an average distance of 2.34 Å and the remainder Ca---O pairs at a distance of 2.54 Å. The calculated intensity curve based on this model was in good agreement with the observed one.     

Structure and properties of the pure and Pr-doped Ge25Ga5Se70 and Ge30Ga5Se65 glasses

The Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ pure and Pr³⁺-doped glasses were prepared by direct synthesis from elements and PrCl₃. It was found that up to 1 mol% PrCl₃ can be introduced in the Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ glasses. Both types of glasses with overstoichiometric and substoichiometric content of Se were homogeneous and of black color. The optical energy gap is E^opt_g=2.10 eV, and the glass transition temperature is T_g=543 K for Ge₂₅Ga₅Se₇₀ and T_g=633 K for Ge₃₀Ga₅Se₆₅. The long-wavelength absorption edge is near 14 μm and it corresponds to multiphonon processes. Doping by Pr³⁺ ions creates absorption bands in transmission spectra, which can be assigned to the electron transitions from the ground ³H₄ level to the higher energy levels of Pr³⁺ ions ³H₅, ³H₆, ³F₂, ³F₃ and ³F₄, respectively. By excitation with YAG:Nd laser line (1064 nm), two intense luminescence bands (1343 and 1601 nm) were excited. The first band can be ascribed to electron transitions between ¹G₄ and ³H₅ energy levels of Pr³⁺ ions. Full width at half of maximum (FWHM) of the intensity of luminescence was found to be 70 nm for (Ge₂₅Ga₅Se₇₀)_1 − x(PrCl₃)_x and (Ge₃₀Ga₅Se₆₅)_1 − x(PrCl₃)_x glasses. The FWHM in selenide glasses is lower than in halide and sulphide glasses. The second luminescence band (1601 nm) can be probably ascribed to the transitions between ³F₃ and ³H₄ energy levels of Pr³⁺ ions. The absorption and luminescence spectra of Pr³⁺ ions in studied glasses are slightly influenced by stoichiometry of glassy matrix. The Raman spectra of studied glasses were deconvoluted and assignment of Raman bands to individual vibration modes of basic structural units was suggested. The structure of studied glasses is mainly formed by corner-sharing and edge-sharing GeSe₄ tetrahedra. The vibration modes of Ga-containing structural units were not found, they are apparently overlapping with Ge-containing structural units due to small difference between atomic weights of Ge and Ga. In the glasses with substoichiometry of Se, the Ge–Ge bonds of Ge₂Se₆ structural units were found. In Se-rich glasses the Se–Se vibration modes were found. In all studied glasses also ‘wrong' bonds between like atoms were found in small amounts. Maximum phonon energy of studied glasses is 320 cm⁻¹.     

Oscillator strength of the infrared absorption band near 1080 cm in SiO2 films

It has been well known that the absorption maximum of the peak near 1080 cm⁻¹ in amorphous SiO₂ films shifts continuously with variation of thickness and properties such as stress. This is a first report on the oscillator strength of the absorption against frequency at the absorption maximum. SiO₂ films on silicon wafers were prepared by thermal growth in either dry O₂ or an O₂/H₂ mixture or liquid-phase deposition in HF saturated with silica gel. The oscillator strength continuously decreased from 1×10⁻⁴ down to 1×10⁻⁵ with the frequency shift from 1099 to 1063 cm⁻¹.     

Mössbauer studies on some glasses and crystals in the Na2O---Fe2O3---SiO2 system

Mössbauer absorption measurements have been made at room temperature on ⁵⁷Fe in iron sodium silicate glasses containing 3–15 mol% Fe₂O₃ and various iron alkali silicate crystals in order to study the state of iron in these glasses. The spectra of all the glasses gave one doublet with a quadrupole splitting varying from 0.73–0.78 mm s⁻¹, while those of Na₂O · Fe₂O₃ · 4 SiO₂ and 5 Na₂O · Fe₂O₃ · 8 SiO₂ crystals showed much smaller quadrupole splitting, 0.28 mm s⁻¹ and 0.10 mm s⁻¹, respectively, and an asymmetrical doublet of much narrower linewidth. When sodium was replaced by other alkali metals of larger size, such as K and Cs, in MFeSi₂O₆ and MFeSi₃O₈ crystals, the quadrupole splitting became wider and approached to 0.73 mm s⁻¹. Such a variation was not observed for glasses. These results suggest that a larger number of non-identical sites exist in iron sodium silicate glasses than in the corresponding crystals.     

Raman spectroscopic investigations of the effect of the doping metal on the structure of binary tellurium-oxide glasses

Raman studies over the range 10 to 1000 cm⁻¹ have been performed on binary tellurium-oxide glasses (1-x)TeO₂-xMO (M = Pb,Zn or Mg) prepared using a conventional melt technique. The intensities and positions of Raman bands observed in the range above 250 cm⁻¹ were found to depend both on the compound oxide and on the amount of doping. Indeed, the ratio of the intensity of the band around 680 cm⁻¹ (assigned to vibrations of TeO₄ trigonal bipyramids) with respect to that of the component around 750 cm⁻¹ (related to stretching-vibrations in TeO₃₊₁, TeO₃ and MO groups) are affected in different ways for the glass-modifier MgO and for the intermediate glass-formers PbO and ZnO. Concurrently, an explicit dependence on the compound oxide and amount of doping was also observed on the maximum of the boson peak (BP) in the low-frequency region around 40 cm⁻¹. The structural correlation lengths in the glasses, calculated using the model described by Shuker and Gammon, were found to be about 0.50 nm (1-x)TeO₂-xMgO glasses and around 0.65 nm for (1-x)TeO₂-xMO (M = Pb or Zn) glasses. All these results are interpreted in terms of the effect of the metal oxide on the changes induced in the structural arrangements of ¹_χ[TeO₄-TeO₃] chains.     

Viscosity matching of new PbF2–InF3–GaF3 based fluoride glasses and ZBLAN for high NA optical fiber

New multicomponent PbF₂–InF₃–GaF₃ bulk glasses have been investigated. They show lower phonon energy (540 cm⁻¹) in comparison with 580 cm⁻¹ for ZBLAN. Large PbF₂ concentration provided glasses with high refractive index up to 1.582 and the viscosity curves revealed an excellent thermal compatibility with ZBLAYN glass. A multimode fiber with a numerical aperture of 0.51, a loss of 0.85 dB/m at 1.3 μm was fabricated using the rotational casting method.     

Effects of ion implantation on intermediate range order: IR spectra of silica

The reflectance spectra of ion implanted SiO₂ glasses has been measured from 5000 cm⁻¹ to 400 cm⁻¹. The silica was implanted with Ti, Cr, Mn, Fe, Cu and Bi to nominal doses ranging from 1×10¹⁵ ions/cm² to 1.2×10¹⁷ ions/cm² at an energy of 160 keV and currents of approximately 2.6 μA/cm². Changes in the intensity of the 1232 cm⁻¹ and 1015 cm⁻¹ vibrational modes are attributed to changes in the intermediate range order (IRO) and to changes in the concentration of non-bridging oxygen (NBO) defects in the implanted layer. These changes are ion and dose dependent. The differing effects on IRO and NBO are attributed to the chemical interaction of the implanted ions with the substrate.     

The Raman spectra of defects in neutron bombarded and Ge-rich vitreous GeO2

This paper reports the polarized Raman spectra of three forms of vitreous GeO₂: the pure glass, neutron irradiated pure glass and unirradiated Ge-rich glass of composition Ge_1.1O₂. The data reveals that the line seen at 520 cm⁻¹ in the pure glass is due to a network defect that is not a Ge---Ge bond and very probably also not an O---O bond. Comparison with spectra of fused silica suggests that the 606 cm⁻¹ defect line seen in v-SiO₂ is not due to Si---Si or O---O bonds.     

Infrared absorption and structure of chlorophosphate glasses

The infrared absorption spectra of glasses in the NaPO₃---ZnCl₂ system were studied in the range of 4000−350 cm⁻¹. The results were interpreted using a local mode approach based on existing frequency charts. A continuous structural breakdown of the glass structure occurs upon addition of ZnCl₂ to the NaPO₃ polymer, with a consequent decrease in its chain length. The actual structure of the chlorophosphate glasses is discussed on the basis of possible anionic groups present. There is evidence for the occurrence of mixed oxychloride coordination shells. The density and glass transition temperature of the glasses were also determined.     

Growth and properties of (Pb0.90La0.10)TiO3 thick films prepared by RF magnetron sputtering with a PbO buffer layer

The (Pb_0.90La_0.10)TiO₃ [PLT] thick films (3.0 μm) with a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering method. The PLT thick films comprise five periodicities, the layer thicknesses of (Pb_0.90La_0.10)TiO₃ and PbO in one periodicity are fixed. The PbO buffer layer improves the phase purity and electrical properties of the PLT thick films. The microstructure and electrical properties of the PLT thick films with a PbO buffer layer were studied. The PLT thick films with a PbO buffer layer possess good electrical properties with the remnant polarization (P_r=2.40 μC cm⁻²), coercive field (E_c=18.2 kV cm⁻¹), dielectric constant (ε_r=139) and dielectric loss (tan δ=0.0206) at 1 kHz, and pyroelectric coefficient (9.20×10⁻⁹ C cm⁻² K⁻¹). The result shows the PLT thick film with a PbO buffer layer is a good candidate for pyroelectric detector.     

An infrared study of crystallization in sodium-disilicate glasses containing iron oxides

The infrared absorption spectra of sodium-disilicate glasses containing various amounts of Fe₂O₃ ([Na₂O · 2 SiO₂]_1−x [Fe₂O₃]_x, where X = 0.05, 0.1 and 0.2) were investigated in the wavenumber range from 200–2000 cm⁻¹. The addition of Fe₂O₃ to the sodium-disilicate glass does not seem to introduce any new absorption band as compared with the spectrum of a pure sodium-disilicate glass; nevertheless, a general shift of the existing absorption bands toward lower wavenumbers is observed. The amount of shift is, in fact, proportional to the content of Fe₂O₃ in the glass. This observation is consistent with the recently proposed structural model for the bonding of Fe³⁺ ions in the iron-sodium-silicate glass system.

Annealing of 20 mol% iron oxide glasses at 550 and 580°C produced an extra sharp infrared absorption peak at about 610 cm⁻¹ wavenumber. This new peak is believed to be related to the crystallized particles of the glass as concluded from both a scanning electron micrograph and an electron diffraction pattern.     

Diffraction study of Li2O·SiO2 glass with computer simulation

The structure of Li₂O·SiO₂ glass has been determined by the pair-function analysis of the radial distribution function (RDF) obtained by X-ray and neutron diffraction measurements. The structure models were constructed by the molecular dynamics method (MD). The calculated RDFs, the summation of the pair-functions of the model, were compared with the observed RDFs while varying the MD parameters. Taking advantage of the negative scattering length of Li for neutron diffraction, the glass structure was investigated in detail, and it was found that the chains of SiO₄ tetrahedra bend at 20 °, which is a little less than for the crystal (23.48 °). It is known that the larger the size of the alkali ions (Na⁺ → K⁺ → Cs⁺), the smaller the bending angle of the chains. It was found that this rule also applies to Li⁺.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

Nuclear magnetic resonance studies of alkaline earth phosphosilicate and aluminoborosilicate glasses

The ¹¹B, ²⁷Al, ²⁹Si and ³¹P magic angle spinning (MAS) NMR spectra of MO–P₂O₅, MO–SiO₂–P₂O₅ and MO(M^′₂O)–SiO₂–Al₂O₃–B₂O₃ (M=Mg, Ca, Sr and Ba, M^′=Na) glasses were examined. In binary MO–P₂O₅ (M=Ca and Mg) glasses, the distributions of the phosphate sites, P(Q_n), can be expressed by a theoretical prediction that P₂O₅ reacts quantitatively with MO. In the ternary 0.30MO–0.05SiO₂–0.65P₂O₅ glasses, the 6-coordinated silicon sites were detected, whose population increases in the order of MgOxCaO–0.05SiO₂–(0.95−x)P₂O₅ glasses, its population increases with an increase in f (=([P₂O₅]−[MO]−[B₂O₃]−[Na₂O])/[SiO₂]) and has maximum at f=9. The signal due to the 5-coordinated silicon atoms is also observed when x is smaller than 0.45. When three network-forming oxides such as SiO₂, Al₂O₃ and B₂O₃ coexist, Al₂O₃ reacts preferably with MO. The populations of 4-coordinated boron atoms, N₄, are expressed well with r/(1−r), where r=([Na₂O]−[Al₂O₃])/([Na₂O]−[Al₂O₃]+[B₂O₃]). The correlation of the Raman signal at 1210 and 1350 cm⁻¹ with the NMR signal of Si(Q₆) at −215 ppm is also seen.     

Infrared study of SiO2 sol to gel evolution and gel aging

The evolution of the gelation of silica gel was studied by means of Fourier transform infrared spectroscopy. The gel was prepared by hydrolysis and polycondensation of tetraethyl orthosilicate in the presence of water with HCl, and with formamide (DCCA) in methanol either added or not. For both systems the gelation process was followed by the time evolution of the ν-Si---O(H) and ν-Si---O(Si) absorption bands. In the systems which used formamide, the ν-Si---O(H) peak shifts from ≈ν = 950 cm⁻¹ for τ = 0 to ≈ν = 968 cm⁻¹ (t = t_gel) and tends to shifts to 975 cm⁻¹ over a long period of time (t = 100t_gel), and a slow rate evolution between 0.1 and 0.4 t_gel is observed. In the absence of formamide the same evolution is observed without the slow rate plateau. For ν-Si-O(Si) absorption bands, the band near 1075 cm⁻¹ remains practically unchanged in both systems during the experiment time, but the second absorption band at 1133 cm⁻¹ is split into two bands each having its own specific evolution, depending on composition and temperature.     

Cation site occupation by Ag/Na ion-exchange in R2O–Al2O3–SiO2 glasses

Ag⁺/Na⁺ ion-exchanged R₂O–Al₂O₃–SiO₂ glasses with uniform concentration profile of Ag⁺ and Na⁺ were prepared by heat treatment in molten silver salt followed by holding at the same temperature in an ambient atmosphere. Their glass transition temperature (T_g) and thermal expansion coefficient (TEC) were measured and structures were investigated using ²⁹Si-MAS NMR, ²⁷Al-MAS NMR, IR and Raman spectroscopies. Both T_g and TEC decreased with increase of the exchange ratio, but T_g was still above the ion-exchange temperature of 400°C even for the fully exchanged sample. The ²⁹Si- and ²⁷Al-MAS NMR spectra were mostly unchanged and no sign of the structural alteration of the glass network was observed. On the other hand, the vibrational spectra showed remarkable peak shifts depending on the exchange ratio. From these structural results, it was found that when the exchange ratio was low, the introduced Ag⁺ ions were stabilized at the non-bridging oxygen (NBO) site, and then Na⁺ ions in AlØ₄ site were exchanged by Ag⁺ ions after full replacement of NBO sites, where Ø represents the bridging oxygen.