Detailed I.R. Study of the Phase Transition in the System AgNO3-Fe(NO3)3

A complete infrared study of the mixed crystal system of AgNO₃ and Fe(NO₃)₃ is carried out in the region 400–4000 cm^?1. The study includes internal fundamental normal vibrations of the NO₃^? ion in the ordered and disordered phases of AgNO₃ at different values of the ferric concentration, I.R. spectra, spectral band shape intensities, and frequencies of the internal modes as functions of the ferric ion concentration. Special attention is paid to bending mode, combination mode, asymmetric stretching mode, and over-tone. The rotational energy barrier is determined at different concentration of the ferric ions in the system of AgNO₃-Fe(NO₃)₃.     

Infrared absorption spectra studies in (NaNO3–NaNO2) system

A complete infrared study of the mixed crystal system of NaNO₃ and NaNO₂ is carried out in the region 600—3000 cm^—1 at room temperature. The study includes fundamental internal normal vibrations of the NO^—₂ and NO^—₃ ions. The IR spectra, spectral band shape intensities, combination modes, and frequencies of the internal modes were studied as a function of NO^—₃ ion concentration. Special attention is paid to the bending mode, the combination mode, and a symmetric stretching mode.     

Indirect electronic transitions in alkali halate crystals-II (sodium bromate and iodate) crystals

In the case of NaClO₃ and KClO₃ crystals, analysis of the long wavelength tail of their fundamental absorption revealed the active participation of the internal vibrations of the chlorate ion (Part I). In order to test the validity of the above interpretation the absorption spectra of two more halates with different anions namely sodium bromate and sodium iodate are analysed in a manner similar to that given in Part I. It is found that the principle internal vibrations of bromate and iodate ions are involved in the indirect transitions. The variation of indirect band gap with temperature is found to be ?2·5 × 10^?4 eV/K and ?2·9 × 10^?4 eV/K for sodium bromate and sodium iodate respectively.     

IR Spectral Analysis of the Mixed Crystal System of AgNO3 and Sr(NO3)2

IR spectroscopy is utilized to analyse the mixed crystal system of AgNO₃ and Sr(NO₃)₂ in the ordered phase II and disordered phases of silver nitrate. The study aims mainly to clearify the change and the affect of partial replacement of Ag⁺ ion by Sr⁺⁺ ion in the mixed crystal system of the two metal nitrates. The change in the rotational energy barrier of the nitrate group was also checked.     

Fabrication and characterization of double-diffused waveguides

An experimental study of two-step Ag⁺/Na⁺ ion exchange in BK-7 glass substrates in molten solutions consisting of AgNO₃/NaNO₃ mixtures is presented. This paper describes a method for evaluating the measured mode index spectra and the index profile of double-diffused semiburied waveguides. They are first diffused at 320°C in 2% melt and are then converted to semiburied waveguides by a second diffusion step consisting of a short-time reimmersion in a 0.25% melt.     

Mössbauer study of spinel system ZnMn1−x Cr x FeO4

Mössbauer effect of the system of spinels ZnMn_1?x Cr _x FeO₄ is studied forx having values 0, 0·2, 0·4, 0·5, 0·6, 0·8 and 1·0. These compounds show quadrupole splitting which increases with increasing Mn³⁺ ion concentration. It abruptly increases at Mn³⁺ ion concentration at which crystal structure also changes.     

Preparation and characterization of sodium binary system (NaI–Na3PO4) inorganic solid electrolyte

New binary inorganic salt such as sodium iodide (NaI)–sodium phosphate (Na₃PO₄) has a great potential to be used as a solid electrolyte, and this solid electrolyte system exhibits high ionic conductivity up to 10^?4 S cm^?1. The solid electrolyte compounds were prepared by mechanical milling followed by pelletizing and sintering at low temperature. The electrical conductivity study was carried out as a function of NaI concentration by impedance spectroscopy technique and the maximum conductivity of (1.02?±?0.19)?×?10^?4 S cm^?1 at room temperature was obtained for the composition 0.50 NaI:0.50 Na₃PO₄. The increase in conductivity is probably due to the increase in number of mobile charge carriers through the conducting pathway provided by tetrahedral structures of Na₃PO₄. The presence of P–O and PO₄ ^3? bands was detected by the infrared technique Fourier transform infrared spectroscopy had been shifted indicating changes in polyhedral structure which in turn led to the formation of conducting channel by corner sharing or through edges. The mobility of the charge carriers in the various compositions of the binary system was investigated by using ²³Na magic angle spinning solid-state nuclear magnetic resonance. The narrowing of the line width ²³Na spectra in the optimum composition of the binary NaI–Na₃PO₄ system can be assigned to Na population with higher ion mobility. X-ray diffraction technique revealed that the addition of NaI resulted in reducing the crystallinity of the samples. Field emission scanning electron microscopy micrographs revealed finer microstructure of the milling samples with grains growth formation and densification upon sintering.     

Potassium cation conduction in K3 − 2x Pb x PO4 solid solutions

New materials of the K_{3 ? 2x} Pb _x PO₄ system with high potassium-cation conductivity have been synthesized and studied. It has been found that the introduction of Pb²⁺ cations substantially increases the conductivity of K₃PO₄ due to the formation of potassium vacancies and the stabilization of the high-temperature cubic structure of the orthophosphate. At low temperatures, the maximum conductivity has been observed in the composition range x = 0.15–0.20 and varies from ～10^?2 S cm^?1 at 400°C to ～10^?1 S cm^?1 at 700°C. The factors influencing the transport properties of the materials under study have been discussed.     

Effect of sodium salts on the cycling performance of tin anode in sodium ion batteries

To determine the effect of electrolyte salts on the cycling properties of tin anodes in sodium ion batteries, sodium/tin cells were prepared using eight electrolytes containing NaCF₃SO₃, NaBF₄, NaClO₄, and NaPF₆ in ethylene carbonate-dimethyl carbonate (EC-DMC) and EC-DMC/fluoroethylene carbonate (FEC) solvents. The first charge capacity and cycling properties strongly depended on the electrolyte salts. Additionally, an appropriately chosen electrolyte salt in combination with the FEC additive improved the cycling properties of the tin electrode. The tin electrode in the presence of the FEC-containing NaPF₆-based electrolyte exhibited the best cycling properties. The first charge capacity and charge capacity after the 45th cycle were 220 and 189 mAh g^?1 _electrode, respectively at a current density of 84.7 mA g^?1 _electrode. The rate performance is also studied using the optimized electrolyte which reveals the ability of the electrode to perform in high current application. At a high current density of 4235 mA g^?1 _electrode, the capacity delivered is 24 mAh g^?1 _electrode. At a current rate of 1694 mA g^?1 _electrode, at the end of 1400th cycle, capacity is about 45 mAh g^?1 _electrode. The results of the study clearly indicate that the electrolyte salts critically affect the electrochemical performance of the tin anode in sodium ion batteries.     

Studies on the complex behavior of optical phonon modes in wurtzite (ZnO)1−x (Cr2O3) x

This paper reports on the use of phonon spectra obtained with laser Raman spectroscopy for the uncertainty concerned to the optical phonon modes in pure and composite ZnO_1?x (Cr₂O₃) _x . Particularly, in previous literature, the two modes at 514 and 640 cm^?1 have been assigned to ZnO are not found for pure ZnO in our present study. The systems investigated for the typical behavior of phonon modes with 442 nm as excitation wavelength are the representative semiconductor (ZnO)_1?x (Cr₂O₃) _x (x = 0, 5, 10 and 15 %). Room temperature Raman spectroscopy has been demonstrated polycrystalline wurtzite structure of ZnO with no structural transition from wurtzite to cubic with Cr₂O₃. The incorporation of Cr³⁺ at most likely on the Zn sub-lattice sites is confirmed. The uncertainty of complex phonon bands is explained by disorder-activated Raman scattering due to the relaxation of Raman selection rules produced by the breakdown of translational symmetry of the crystal lattice and dopant material. The energy of the E ₂ (high) peak located at energy 53.90 meV (435 cm^?1) due to phonon–phonon anharmonic interaction increases to 54.55 meV (441 cm^?1). A clear picture of the dopant-induced phonon modes along with the B ₁ silent mode of ZnO is presented and has been explained explicitly. Moreover, anharmonic line width and effect of dislocation density on these phonon modes have also been illustrated for the system. The study will have a significant impact on the application where thermal conductivity and electrical properties of the materials are more pronounced.     

Transformations of radicals and ions in irradiated sodium sulfate doped with nitrate ions

The structure and properties of the paramagnetic centers formed by γ-irradiation at 77 K in sodium sulfate doped with nitrate ions have been investigated by the EPR method. The NO^2? ₃, NO₂ and SO^? ₄ radicals have been identified. The orientation of NO^2? ₃ relation to crystallographic axes is determined. In the 77-400 K temperature range the transformations of observable radicals have been studied. The mechanisms of their formation and thermal annealing have been discussed. The symmetry of nitrate ions in sodium sulfate was investigated by diffuse reflectance infrared Fourier transform spectroscopy. At the concentration of NO^? ₃ up to 5.5 × 10¹⁸ g^?1 the nitrate ion was supposed to have a planar or pyramidal configuration of the D_3h or C_3V symmetries. At the concentration of the dopant higher than 5.5 × 10¹⁸ g^?1 the nitrate ions with the C_2V symmetry were observed.     

Na+ ion conductivity and crystallographic cell characterization in the Hf-nasicon system Na1+xHf2SixP3−xO12

We have measured the effect of varying the mobile ion concentration on the sodium ion conductivity in the Hf-Nasicon system, Na_1+xHf₂Si_xP_3-xO₁₂, for 1.4 ? x ? 2.8. The conductivity is greatest for Na_3.2Hf₂Si_2.2 P_0.8O₁₂: σ_25°C = 2.3 × 10^?3 (ω cm)^?1, and σ_250°C = 1.7 × 10^?1 (ω cm)^?1. These values are approximately 50% greater and worse, respectively, than the values reported for the best Zr-Nasicon. We have characterized the variation of lattice parameters with composition and found the behavior to be similar to that of Zr-Nasicon. A small distortion from rhombohedral to monoclinic symmetry occurs for compositions 1.8 ? x ? 2.2.     

Effect of sodium citrate as complexing on electrochemical behavior and speciation diagrams of CoFeNiCu baths

In this study, the effects of addition of sodium citrate dosages and different pH levels on the electrochemical behavior of CoFeNiCu alloy baths (electrolytes containing metal ions) were investigated. Stability (Pourbiax) diagrams and also speciation diagrams of cobalt, iron, nickel and copper, in conventional and citrate-added CoFeNiCu bath, were calculated by ChemEQL V.3.0 software. Stability diagrams showed that addition of 20 g?L^?1 sodium citrate to the bath increased the pH of formed detrimental metal hydroxides (especially Fe(OH)₃ from pH 3.4 to pH?~?6.9) through forming stable complexed species that were more stable than metal hydroxides at low pH levels (< ~3). According to the speciation diagrams, both pH level and sodium citrate dosage had noticeable effect on the distribution of species in the baths. Generally, at low pH level and/or sodium citrate dosage, Co⁺⁺, Fe⁺⁺, Ni⁺⁺, and Cu⁺⁺ species were dominant. The concentration of complexed species of Co(C₆H₅O₇)^? ( at pH?>?~ 7.5 or sodium citrate dosage?>?~ 30 g?L^?1), Fe(C₆H₅O₇)^? (at pH?>?~ 5.5 or sodium citrate dosage?>?~ 25 g?L^?1), Ni(C₆H₅O₇)^? (at pH?>?~ 6 or sodium citrate dosage?>?~ 30 g?L^?1), and Cu(OHC₆H₅O₇)^2? ( at pH?>?~ 8 or sodium citrate dosage?>?~ 20 g?L^?1) became significant. The effects of sodium citrate and reverse potential (E _λ) on cyclic voltammetry curves were also studied. The addition of sodium citrate in the bath shifted the reduction potential of metals towards more negative potentials. Moreover, in order to deposit cobalt, iron, and nickel simultaneously with copper, it was necessary to increase E _λ value gradually with sodium citrate dosage; otherwise, only copper would have deposited from citrate-added CoFeNiCu bath. The study of speciation diagrams showed that reduction of metals from CoFeNiCu bath with natural pH (no acid or base is added to adjust pH and it was?~?5.2) and containing 20 g?L^?1 of sodium citrate mainly occurred directly from complexed species.     

IR Spectroscopic Study of the Mixed Crystal System (LixAg1-x)NO3

A spectroscopic analysis of the various IR internal modes for the mixed crystal system of lithium nitrate and silver nitrate were carried out. The study aims mainly to find out the effect of partial replacement of Ag⁺ ion by Li⁺ ion on the internal fundamental modes of vibrations of the NO₃^? group in both of the ordering and disordering states of these two metallic nitrate compounds. The characteristic variations observed are attributed to differences in polarizability from cationic sphere around the nitrate group. An interesting increase of the maximum frequency observed on passing from pure components to mixtures is attributed to a change in force constant.     

Silicon negative ion implantation induced vacancy defects in thermally grown SiO2 thin films

ABSTRACT

Thermally grown SiO₂ thin films on a silicon substrate implanted with 100?keV silicon negative ions with fluences varying from 1?×?10¹⁵ to 2?×?10¹⁷ ions cm^?2 have been investigated using Electron spin resonance, Fourier transforms infrared and Photoluminescence techniques. ESR studies revealed the presence of non-bridging oxygen hole centers, E′-centers and P_b-centers at g-values 2.0087, 2.0052 and 2.0010, respectively. These vacancy defects were found to increase with respect to ion fluence. FTIR spectra showed rocking vibration mode, stretching mode, bending vibration mode, and asymmetrical stretching absorption bands at 460, 614, 800 and 1080?cm^?1, respectively. The concentrations of Si–O and Si–Si bonds estimated from the absorption spectra were found to vary between 11.95?×?10²¹ cm^?3 and 5.20?×?10²¹ cm^?3 and between 5.90?×?10²¹ cm^?3 and 3.90?×?10²¹ cm^?3, respectively with an increase in the ion fluence. PL studies revealed the presence of vacancies related to non-bridging oxygen hole centers, which caused the light emission at a wavelength of 720?nm.     

Proton and Li-7 NMR study on the effect of the OH− anion upon the Li+-ion conduction in the solid solution Li5NI2LiOH

From ¹H and ⁷LiNMR relaxation times T₁, T₂ and T_1ρ in Li₅NI₂ and the solid solution Li₅NI₂?0.77LiOH, the diffusive motion of the Li⁺ ion was studied to make clear the role of the OH^? ion in improving the Li⁺ ionic conduction. At temperatures as low as 140 K, each Li⁺ ion jumps among four available positions. Its activation energies are 9.26 and 11.8 kJ mol^?1 for Li₅NI₂ and Li₅NI₂?0.77LiOH, respectively. Diffusive motion was observed in T₂ and T_1ρ above 240 K. The mode of the cation distribution and the diffusion mechanism are not affected by the presence of the OH^? anion. The most noticeable fact is that the OH^? ion is substituted selectively for the N^3? ion that is the nearest neighbour of the Li⁺ ion. This selective substitution increases the concentration of the Li⁺ vacancy most effectively up to 4.2% of the total Li positions. At the same time it diminishes the strong attractive force of the N^3? anion binding the Li⁺ ion to the position, and thus the activation energy. For the diffusion, an anomalously low attempt frequency of 3&#x0303; × 10⁹Hz was obtained from T_1ρ, while the normal value of 4.8 × 10¹²Hz was obtained from the ionic conductivity. The large discrepancy was attributed to the collective nature of the Li⁺ diffusive motion.     

Determination of the negative ion yield of copper sputtered by cesium ions

Abstract

This paper describes the determination of secondary ion yields for negative ions obtained by bombardment of copper by cesium ions. Stable and reproducible surface conditions are reached by high rate sodium deposition simultaneously with sputtering. An optimum thickness of sodium corresponding to about one monolayer is found. Total negative ion yields K ^? _Σ are measured by a double modulation technique. Individual negative ion yields K ^? _i are then found by mass spectrometrically determining the various negative ion intensities, the sum of which relates linearly to K ^? _Σ. This method is based on the assumption of an equal angular and energy distribution of all sputtered negative ions. Data are given for K^? _Σ and K ^? _Cu and K^? _O. The dependence of K ^? _i on primary ion energy (500 to 2500 eV) is similar to ordinary sputtering which points to the same basic mechanism in both cases.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Ge Nanoparticles Encapsulated in Interconnected Hollow Carbon Boxes as Anodes for Sodium Ion and Lithium Ion Batteries with Enhanced Electrochemical Performance

A carbothermal reaction route to Ge nanoparticle homogeneously encapsulated hollow carbon boxes from NH₄H₃Ge₂O₆/resorcinol formaldehyde precursors is designed, using NH₄H₃Ge₂O₆ as a Ge precursor from commercial GeO₂ and NH₄OH. The Ge/C hybrid anode for sodium ion battery displays a higher Na⁺ storage capacity of 346 mA h g^?1 after 500 cycles at a current density of 100 mA h g^?1, almost approaching the theoretical capacity of Ge. Furthermore, Ge/C anode shows significantly improved electrochemical performance for Li⁺ storage, showing a higher initial Coulombic efficiency of 85.1% and a superior reversible capacity of 1336 mA h g^?1 at a high current density of 200 mA g^?1 after 150 cycles. An excellent rate capability with a capacity of 825 mA h g^?1 at a current density of 4.0 A g^?1 can be obtained based on Ge/C anodes. The enhanced electrochemical performance can be attributed to the unique microstructures of Ge/C hybrid anode. The internal void space of hollow carbon boxes can accommodate the volume expansion of Ge during lithiation or sodiation process, thus preserving the structural integrity of electrode material. The interconnected carbon shell can increase the electronic conductivity of the electrode, resulting in the high rate capability and cycling stability.     

Amplifying Characteristics of Er3+/Yb3+ Co-Doped Parallel-Cascaded Double Microring Resonators

Abstract

In terms of the coupled mode theory, formulas of the transfer function and the output power gain are presented for an Er³⁺/Yb³⁺ co-doped parallel-cascaded double microring resonator. Around the pump wavelength of 0.98 μm and the central signal wavelength of 1.55 μm, analysis is performed for the dependence of the output power gain on the pump power, signal power, dopant concentration, amplitude coupling ratio, and ring spacing. The results show that the output power gain of this device is much larger than that of the Er³⁺/Yb³⁺ co-doped waveguide amplifier with identical waveguide lengths. In the case of the amplitude coupling ratio κ = 0.064, ring spacing L₂ = 10π R, pump power P_p0 = 8 mW, signal power P_s0 = 37.2 μW, Er³⁺ ion concentration N_Er = 1 × 26 m^?3, and Yb³⁺ ion concentration N_Yb = 3 × 27 m^?3, the device can produce higher signal power gain from 11.9 dB even up to 70 dB.