Structural characterization of ionomer glasses by multinuclear solid state MAS-NMR spectroscopy

In the present study we report the results of ²⁹Si, ²⁷Al, ³¹P and ¹⁹F magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) of 4.5SiO₂-3Al₂O₃-1.5P₂O₅-(5−z)CaO-zCaF₂ glasses with z = 0-3 to elucidate the effect of fluoride content on the glass structure. The ²⁹Si MAS-NMR spectra gave a chemical shift of about −90 ppm corresponding to Q³(3Al) and Q⁴(3Al). The ²⁷Al MAS-NMR showed a large broad central peak around 50 ppm, which is assigned to four-coordinated Al linked via oxygen to P. A shoulder around 30 ppm and a small peak at about 0 to −10 ppm appeared in the ²⁷Al MAS-NMR spectra of the glasses on increasing the fluoride content assigned to five-coordinated and six-coordinated Al species, respectively. The ³¹P MAS-NMR spectra indicated the presence of Al-O-P bonds. The ³¹P chemical shift decreased with increasing fluoride content as a result of calcium being complexed with fluoride. This resulted in a reduction of the number of available cations to charge balance non bridging oxygens in phosphorus and an increase in the number of Al-O-P bonds being formed, instead. The ¹⁹F spectra indicated the presence of Al-F-Ca(n) and F-Ca(n) species in all the glasses containing fluoride as well as an additional Si-F-Ca(n) species in the glasses with higher fluoride content.     

Detecting a true quantum pump effect

Reflectance measurements from p-type GaSb:Zn epitaxial films with different hole concentrations (10¹⁷–10¹⁸ cm^-3) have been investigated over the frequency region of 100–1000 cm^-1. A minimum broadening feature corresponding to the hole plasmon was observed in the reflectance spectra. The experimental infrared spectra were well fitted using a Lorentz-Drude dispersion model. The real part ε₁ of the dielectric function decreases with increasing hole concentration. However, the imaginary part ε₂ increases with hole concentration in the far-infrared region. This indicates that the acoustic- and optic-phonons mainly participate in the free carrier absorption processes. The hole mobility obtained from Hall-effect measurements is slightly larger than that derived from optical measurements and the average ratio of mobilities is estimated to be 1.33. Owing to overdamping effects, the upper branch of longitudinal-optical phonon plasmon (LPP) coupled modes was observed. The upper LPP⁺ frequency increases with hole concentration and it shows a transition from phonon-like to plasmon-like behavior. A theoretical analysis with solutions in the complex frequency plane describes these experimental results.     

Interatomic potential effects on dynamical heterogeneities in liquid SiO2

Dynamical heterogeneities (DH) in low density liquid SiO₂ have been investigated by molecular dynamics (MD) method. Simulations were done in the basic cube under periodic boundary conditions containing 3000 particles with the pair interatomic potentials, which have a weak electrostatic interaction and a Morse type short range interaction (PMSI). We have evaluated the non-Gaussian parameter for the self part of the van Hove correlation function and we found a clear evidence of the existence of DH in low density liquid SiO₂. Moreover, the atomic displacement distribution (ADD) in a model has been obtained and it deviates from a Gaussian form. The results have been compared with those obtained in another liquid SiO₂ system with the Born-Mayer interatomic potentials (BMP) in order to observe the interatomic potential effects on the DH in the system and indeed, the effects are strong. Calculations showed that particles of extremely low or fast mobility have a tendency to form a cluster and mean cluster size of most mobile and immobile particles in PMSI models increases with decreasing temperature. In contrast, no systematic changes have been obtained for the most mobile and immobile particles in BMP models. Calculations show that there is no relation between local particle environment and particle mobility in the system.     

Preparation of pulse plated GaAs films

Thin GaAs films were prepared by pulse plating from an aqueous solution containing 0.20 M GaCl₃ and 0.15 M As₂O₃ at a pH of 2 and at room temperature. The current density was kept as 50 mA cm⁻² the duty cycle was varied in the range 10-50%. The films were deposited on titanium, nickel and tin oxide coated glass substrates. Films exhibited polycrystalline nature with peaks corresponding to single phase GaAs. Optical absorption measurements indicated a direct band gap of 1.40 eV. Photoelectrochemical cells were made using the films as photoelectrodes and graphite as counter electrode in 1 M polysulphide electrolyte. At 60 mW cm⁻² illumination, an open circuit voltage of 0.5 V and a short circuit current density of 5.0 mA cm⁻² were observed for the films deposited at a duty cycle of 50%.     

Combinatorial ion beam synthesis of CdSxSe1−x nanocrystals

In this presentation we focus on the synthesis of buried multielemental semiconductor nanoparticles by sequential high dose ion implantation and post-implantation annealing. Nanocluster formation and alloying was studied by Raman-, Rutherford Backscattering Spectroscopy (RBS) and X-ray diffraction analysis (XRD) on a materials library of CdS_xSe_1−x nanoclusters buried in thermally grown SiO₂ on silicon. Characteristic peak shifts of the LO-Raman signal and XRD-peaks due to varying S- and Se-fraction indicate that the ion beam synthesized clusters consist of a solid solution of Cd, S and Se. In addition the influence of the implanted dose ratios on the structural evolution of the nanocluster-SiO₂ system will be discussed.     

The ultimate in real-time ellipsometry: Multichannel Mueller matrix spectroscopy

A review of the techniques and applications of multichannel ellipsometry in the dual-rotating-compensator configuration is given. This ellipsometric approach has been established as the ultimate in real-time, single-spot optical measurement, as it determines the entire 16-element Mueller matrix of a sample over a wide spectral range (up to 1.7-5.3 eV) from raw data collected over a single optical period of 0.25 s. The sequence of optical elements for this ellipsometer is denoted PC_1rSC_2rA, where P, S, and A represent the polarizer, sample, and analyzer. C_1r and C_2r represent two MgF₂ rotating compensators, either biplates or monoplates that rotate synchronously at frequencies of ω₁ = 5ω and ω₂ = 3ω, where π/ω is the fundamental optical period. Previous high-speed Mueller matrix measurements with this instrument have been performed on uniform, weakly anisotropic samples such as (110) Si, in which case one can extract the bulk isotropic and near-surface anisotropic optical responses simultaneously. In such an application, the instrument is operated at its precision/accuracy limits. Here, ex situ results on a strongly anisotropic, locally biaxial film are presented that demonstrate instrument capabilities for real-time analysis of such films during fabrication or modification. In addition, the use of the instrument as a real-time probe to extract surface roughness evolution on three different in-plane scales for an isotropic film surface is demonstrated for the first time.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Structural investigations of GeS2-Ga2S3-CdS chalcogenide glasses using Raman spectroscopy

Raman investigations were carried out for various compositions of chalcogenide glasses in the GeS₂-Ga₂S₃-CdS system. Addition of Ga₂S₃ into GeS₂ results in the formation of metal-metal bonds and edge-shared GaS_4/2 tetrahedra. Ge²⁺ ions may surround [GaS_4/2]¹⁻ tetrahedra acting as charge compensators. Upon the addition of CdS into the GeS₂-Ga₂S₃ system, the number of the metal-metal bonds and edge-shared GaS_4/2 tetrahedra decreases, resulting in the formation of corner-shared tetrahedra with non-bridging sulfurs (NBS). Cd²⁺ ions can be dissolved into the glass network as charge compensators for these NBS and exited few [GaS_4/2]¹⁻ tetrahedra. The high solubility of CdS is ascribed to the dissociation of metal-metal bonds and edge-shared tetrahedra in these Ga-containing glasses.     

Extended rigidity percolation and chemical thresholds in Ge-Te-Pb glasses as revealed by MDSC

Thermal analysis of Ge₂₀Te_80−xPb_x (2≤x≤8) glasses has been undertaken using modulated differential scanning calorimetry (MDSC). The compositional dependence of thermal parameters is investigated. The crystallization temperatures (T_c) estimated from the total heat flow show detectable changes at compositions x=4, 6.5 and 7.5. Further, the heat capacity change at the glass transition temperature, measured from the reversible heat flow curve (ΔC_p^R), is found to exhibit a maximum and an inflexion at compositions x=4 and 6.5 and minimum at x=7.5, respectively. Also, the relaxation enthalpy, estimated from the area under the non-reversing heat flow curve (ΔH^NR), exhibits similar features at the said compositions. From the observed MDSC results, it has been proposed that the compositions x=4 and x=6.5 denote to the onset and completion of rigidity percolation and x=7.5 corresponds to the chemical threshold of the system.     

Absorption and emission properties of Nd in lithium cesium mixed alkali borate glasses

Lithium cesium mixed alkali borate glasses of the composition 67B₂O₃·xLi₂O·(32−x)Cs₂O (where x=8, 12, 16, 20 and 24) containing 1 mol% Nd₂O₃ were prepared by melt quenching. The absorption spectra of Nd³⁺ were studied from the experimental oscillator strengths and the Judd-Ofelt intensity parameters were obtained. The intensity parameters are used to determine the radiative decay rates (emission probabilities of transitions) (A_T), branching ratios (β) and integrated absorption cross-sections (Σ) of the Nd³⁺ transitions from the excited state J manifolds to the lower lying J′ manifolds. Radiative lifetimes (τ_R) are estimated for certain excited states of Nd³⁺ in these mixed alkali borate glasses. Luminescence spectra were measured and the emission cross-sections (σ_p) were evaluated for the three emission transitions. The variation of luminescence intensity with x was recorded for the three transitions at different excitation power to see the effect of mixed alkalies in these borate glasses.