Preparation of Cu2ZnSnS4 single crystals from Sn solutions

We investigated the phase diagrams of the Cu₂ZnSnS₄ (CZTS)–Sn pseudobinary system in order to obtain knowledge useful for the growth of high-quality CZTS single crystals using a solution-based method. For Sn solutions saturated with less than ～60 mol% CZTS, the solutes are separated into two phases (CZTS phase+SnS_x phase+liquid phase). On the other hand, for solutions with more than 60 mol% CZTS, the solutes are single phase (CZTS phase+liquid phase). The CZTS single crystals were obtained from a 70 mol% CZTS solution (liquid temperature 850 °C) at 900 °C. The powder X-ray diffraction (XRD) pattern of the CZTS single crystal shows preferred orientations of (112), (220) and (312) planes, confirming the Kesterite structure of CZTS. The Raman spectrum shows three peaks at 287, 338, 371 cm^?1, which corresponded to CZTS peaks. The composition of the CZTS single crystal along the growth direction is found to be slightly Cu-poor, Zn-rich and S-rich. Therefore, it is assumed that the Cu vacancy is the dominant p-type conduction mechanism.     

Protein–solvent interaction in urea–water systems studied by dielectric spectroscopy

Dielectric spectroscopy measurements were performed at 298 K for bovine serum albumin (BSA) dissolved in aqueous solutions of urea (0–9  M with steps of 1 M). It was shown that unfolding of BSA molecules by urea influenced the dynamic structures of water and urea molecules, and consequently changed their dielectric responses. At low urea concentrations (0–5 M), unfolding of BSA molecules is not very significant and mainly the globular surface of the BSA interacts with the solvent molecules. In comparison with urea solutions without BSA, the high frequency dielectric spectrum (γ-dispersion) was significantly broadened with addition of the BSA, although the characteristic frequency was not affected much. Such behavior is similar to that reported for aqueous solutions of synthetic polyelectrolytes. At high urea concentrations (6–9 M), significant unfolding of the BSA molecules occurred, exposing the hydrophobic side chains to the solvent and likely increasing the effects of hydrophobic hydration. As a result, the dielectric response of the solvent molecules was found to be more complicated.     

Dielectric properties of keratin–water system in diabetic and healthy human fingernails

Dielectric measurements as a function of temperature (22–200 °C) and frequency (100 Hz–100 kHz) are reported for the healthy and the diabetic nail plate. The plots of the relative permittivity versus temperature at the same frequency are higher in the healthy than in the diabetic nail. These results are interpreted as caused by the damage of the polar sites in the keratin–matrix–water system of the diabetic nail. The activation energy of the β-relaxation is higher for the diabetic nail than for the healthy nail, suggests that advanced glycation end products (AGEs) may form cross-links by interaction with keratin. The results of this work indicate that the dielectric measurements of the nail could be used in detection of diabetes.     

Surface morphology of spin-coated As–S–Se chalcogenide thin films

Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d ∼ 100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with R_q values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm⁻¹) and C–H (at 2965, 2935 and 2880 cm⁻¹) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures T_g = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.     

Exploration on nano-composite fumed silica-based composite polymer electrolytes with doping of ionic liquid

Fumed silica (SiO₂)-based composite polymer electrolytes were prepared by means of solution casing technique. Horizontal attenuated total reflectance-Fourier Transform Infrared (HATR-FTIR) study shows the complexation between polymer matrix and SiO₂. The highest ionic conductivity of (4.11 ± 0.01) × 10^? 3 Scm^? 1 is achieved upon inclusion of 8 wt.% of SiO₂. Three different regions have been observed in the frequency dependence–ionic conductivity study. The conductivity rises sharply with frequency at low frequency regime. It is followed by a frequency independent plateau region and sharp decrease in the conductivity at high frequency range. The dielectric permittivity (ε^') and dielectric loss (ε^") are decreased with increasing the frequency. This phenomenon is mainly attributed to the electrode polarization effect. The formation of electrical double layer has been proven in these dielectric permittivity studies. This indicates the non-Debye properties of the nano-composite polymer electrolytes.     

Vacuum-deposited poly(o-methoxyaniline) thin films: Structure and electronic properties

Thin poly(o-methoxyaniline) (POMA) films have been formed by thermovacuum deposition in the temperature range of 350–450 °C and at a pressure of 5 × 10^?5 Torr. The structure properties of vacuum deposited POMA films according to FTIR and UV–VIS spectra are similar to those observed for the emeraldine form of polyaniline. Current–voltage characteristics (I–V) of sandwichtype device ITO/POMA/A1 possess rectifying properties with the ideality factor ≈4 at room temperature. On the basis of the dependence of conductivity on frequency in the frequency range of 10 Hz to 1 MHz, it is shown that the Pollack–Pohl current flow hopping mechanism dominates in a polymer film; such mechanism is typical of non-ordered systems.     

Preparation,vibrational structure and dielectric properties studies of cotton linter and its derivatives

Preparation of unhydrolyzed and hydrolyzed cotton linters as well as their derivatives (carboxylate, phosphate and phosphosulphonate), vibrational structure and dielectric properties were studied in this work. The vibrational modes were analyzed by FTIR spectroscopy and the band at 1730 cm^?1 in the carboxylation of unhydrolyzed and hydrolyzed was appeared due to introduce of carboxylic group. The new bands appeared at 1208 and 1400 cm^?1 in the phosphorylation and phosphosulphonation assigned to C–O–P and C–O–S, respectively. The data indicated that, new chemical structure for the derivatives of unhydrolyzed and hydrolyzed cotton linter was formed. The crystallinity index (CrI) was measured from absorbance ratio of the band 1428 and 900 cm^?1. The real part of dielectric constant (ε′) and AC electrical conductivity was studied in the temperature range (295–375 K) at two different frequencies, 800 and 2000 kHz. The ε′ was decreased with increasing frequency due to dispersion. The frequency–temperature dependent conductivity and mechanisms of the electronic conduction were discussed.     

Characterization of chitosan/PVA blended electrolyte doped with NH4I

The (chitosan–PVA)–NH₄I electrolytes have been prepared by the solution casting method. The prepared electrolytes are analyzed using Fourier transform infrared (FTIR) spectroscopy in order to determine the interaction between salt and the polymer blend hosts which can be deduced from the band shifting. From infrared spectra, shifts are observed at the amine, carboxamide, carbonyl and hydroxyl bands of chitosan and PVA. These shifts indicate that complexation has occurred. The crystallinity/amorphousness of the blended electrolytes has been examined by X-ray diffraction (XRD). XRD pattern shows that the crystallinity of chitosan–NH₄I electrolyte increases with PVA concentration. Impedance of the electrolytes has been measured using electrochemical impedance spectroscopy (EIS) over the frequency range from 50 Hz to 1 MHz. The highest conducting sample 55 wt.% (chitosan–PVA)–45 wt.% NH₄I has conductivity of 1.77 × 10^? 6 S cm^? 1. The chitosan:PVA ratio is 1:1. This is higher than the conductivity for the unblended electrolyte 55 wt.% chitosan–45 wt.% NH₄I which is 3.73 × 10^? 7 S cm^? 1. From ln τ versus 10³/T plot, the activation energy for relaxation process is 0.87 eV. This is different from activation energy for dc conductivity which is 0.38 eV. Ion conduction is by hopping.     

Electrical characterizations of silver chalcogenide glasses

We present a study of the electrical properties of silver chalcogenide glasses ‘40AgI’–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂ and 50AgI–25Ag₂S–25GeS₂ in the 77–400 K temperature and the 20 Hz to 1 MHz frequency ranges. In our temperature range, a large variation of the real permittivity is observed, in relation with an electrodes polarization effect. As the amount of silver iodide increases in the Ag₂S–GeS₂ matrix, the glass transition temperature and the activation energies decrease, the electrical conductivity increases and reaches 4 Ω⁻¹ m⁻¹ at room temperature for the glass with 50% AgI. The study of the conductivity shows a behavior due to a high ionic conductivity, thermally activated with E_dc = 0.21 eV, E₁ = 0.075 eV (40AgI–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂), E_dc = 0.17 eV, E₁ = 0.055 eV for 50AgI–25Ag₂S–25GeS₂. For these glasses, we have seen three conductivity regimes. The first two terms are thermally activated. The third term cannot be actually clearly identified because either it is thermally activated with a very low activation energy and frequency dependent, or it is almost non-thermally activated and frequency dependent.     

Effect of the ytterbium concentration on the upconversion luminescence of Yb3+/Er3+ co-doped PbO–GeO2–Ga2O3 glasses

The effect of Yb³⁺ concentration on the frequency upconversion (UPC) of Er³⁺ in PbO–GeO₂–Ga₂O₃ glasses is reported for the first time. Samples were prepared with 0.5 wt% of Er₂O₃ and different concentrations of Yb₂O₃ (1.0–5.0 wt%). The green (523 and 545 nm) and red (657 nm) emissions are observed under 980 nm diode laser excitation. The dependence of the frequency UPC emission intensity upon the excitation power was examined and the UPC mechanisms are discussed. An interesting characteristic of these glasses is the increase of the ratio of red to green emission, through an increase of the Yb³⁺ concentration due to an efficient energy transfer from Yb³⁺ to Er³⁺.     

Conductivity and dielectric properties of polyvinyl alcohol–polyvinylpyrrolidone poly blend film using non-aqueous medium

Several methods such as copolymerization, plasticization and blending etc., have been used to modulate the conductivity of polymer electrolytes. Polymer blending is one of the most important contemporary ways for the development of new polymeric materials and it is a useful technique for designing materials with a wide variety of properties. Polymer blend electrolyte has been prepared with different concentrations of PVA and PVP by solution casting technique using DMSO as solvent. The prepared films have been investigated by different techniques. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis reveals that the interchain hydrogen bonding within a PVA–PVP blends. The dielectric permittivity (ε*) and modulus (M*) have been calculated from the ac impedance spectroscopy in the frequency range 42 Hz– 1 MHz and the temperature range 308–373 K. The maximum conductivity has been found to be 1.58 × 10^? 6 S cm^? 1 at room temperature for 70PVA:30PVP concentration. The conductivity has been increased to 5.49 × 10^? 5 S cm^? 1 when the temperature is increased to 373 K. The activation energy of all samples was calculated using the Arrhenius plot and it has been found to be 0.53 eV to 0.78 eV.     

Effect of silver doping on the electrical properties of a-Sb2Se3

This paper reports the effect of Ag-doping on electrical properties of a-Sb₂Se₃ in the temperature range 230–340 K and frequency range 5–100 kHz. The variation of transport properties with thermal doping has been studied. Ag-doping produces two homogeneous phases in the sample, which are found to be voltage dependent in the temperature range studied and frequency dependent in lower frequency region (0.1–10 kHz). Activation energy E_g and C′ [= σ₀ exp (γ/k), where γ, is the temperature coefficient of the band gap] calculated from dc conductivity has been found to vary from (0.42 ± 0.01) eV to (0.26 ± 0.01) eV and (4.11 ± 0.01) × 10⁻⁵ to (2.90 ± 0.02) × 10⁻⁶ Ω⁻¹ cm⁻¹ respectively. Ag-doping can be used to make the sample useful in device applications.     

Visible to near-infrared down-conversion luminescence in Tb3 + and Yb3 + co-doped lithium–lanthanum–aluminosilicate oxyfluoride glass and glass-ceramics

Tb^3 + and Yb^3 + co-doped oxyfluoride glasses were fabricated in a lithium–lanthanum–aluminosilicate matrix (LLAS) by a melt-quench technique. Glass-ceramics were obtained by appropriate heat treatment of the as-prepared glasses. Visible to near-infrared down-conversion luminescence was studied for glass and glass-ceramic samples with different Yb^3 + concentrations. It has been found that the luminescence intensity at 940–1020 nm from Yb^3 + ions increases while the emission lifetime of Tb^3 + ions decreases in the glass-ceramic compared to that in the as-prepared glass, which indicates that the energy transfer efficiency increases in the glass-ceramics compared to that in the as-prepared glass. The down-conversion luminescence also increased for increasing Yb^3 + concentration from 1 mol% to 2 mol%, but decreased for the sample with a high Yb^3 + co-doping concentration of 8 mol%, which is attributed to the concentration quenching.     

The effect of different oriented sapphire substrates on the growth of polar and non-polar ZnMgO by MOCVD

Polar and non-polar ZnMgO were synthesized on different crystallographic planes (C-, R- and M-planes) of sapphire (Al₂O₃) substrates by metal organic chemical vapor deposition, respectively. Under the same experimental condition, polar ZnMgO nanorods were obtained on C-Al₂O₃ substrate whereas non-polar ZnMgO thin films were obtained on R- and M-Al₂O₃ substrates. The surface morphology was significantly influenced by the competition of the preferable growth directions on different sapphire substrates. On C-Al₂O₃ substrate, ZnMgO nanorods were vertically well-aligned with typical lengths in the range 330–360 nm. On R- and M-Al₂O₃ substrates, however, ZnMgO thin films with flat surfaces were obtained, whose thickness were 150 and 20 nm, respectively. Under the same condition, the C-ZnMgO deposited on C-Al₂O₃ substrate has the maximum growth velocity (11 nm/nim), followed by A-ZnMgO deposited on R-Al₂O₃ substrate (5 nm/min), and the M-ZnMgO deposited on M-Al₂O₃ substrate has the minimum one (0.67 nm/min). The Near-Band-Edge (NBE) emission in Photoluminescence (PL) spectra shows a clear blueshift and a slight broadening compared with that of pure ZnO samples, which suggest that the Mg content has successfully incorporated into ZnO. The different energy blueshifts (67 meV and 98 meV) of the NBE emission demonstrate that A-ZnMgO deposited on R-Al₂O₃ substrate has higher Mg incorporation efficiency than C-ZnMgO on C-Al₂O₃ substrate.     

Photocapacitance measurements in irradiated a-Si:H based detectors

Photocapacitance measurements were performed on amorphous silicon p–i–n detectors before and after particle irradiation with 1.5 MeV 4 He⁺ ions. The spatial resolution across a degraded spot is similar to the one obtained in photocurrent scans and is of the order of the diameter of the scanning laser beam. We monitored the transient capacitance after applying short laser pulses to deduce trap energies of 0.64 eV. Photocapacitance measurements as a function of the applied bias, the measurement frequency up to 1 MHz, and the wavelength of laser light are discussed. The reduction in photocapacitance signal and the shift of the cut-off frequency after ion bombardment are correlated with the change in transport properties.     

Fluorine laser-induced silicon hydride Si–H groups in silica

Formation and destruction of silicon hydride (Si–H) groups in silica by F₂ laser irradiation and their vacuum ultraviolet (VUV) optical absorption was examined by infrared (IR) and VUV spectroscopy. Photoinduced creation of Si–H groups in H₂-impregnated oxygen deficient silica is accompanied by a growth of infrared absorption band at 2250 cm⁻¹ and by a strong increase of VUV transmission at 7.9 eV. Photolysis of Si–H groups by 7.9 eV photons in this glass was not detected when the irradiation was performed at temperature 80 K. However, a slight destruction of Si–H groups under 7.9 eV irradiation was observed at the room temperature. This finding gives a tentative estimate of VUV absorption cross section of Si–H groups at 7.9 eV as 4 × 10⁻²¹ cm², showing that Si–H groups do not strongly contribute to the absorption at the VUV fundamental absorption edge of silica glass.     

The role of vanadium valence states and coordination on electrical conduction in lithium iodide borate glasses mixed with small concentration of silver iodide

LiI–AgI–B₂O₃ glasses mixed with different concentrations of V₂O₅ (ranging from 0 to 1.0 mol%) were prepared. Electrical and dielectric properties over wide ranges of frequency (10^?2–10⁷ Hz) and temperature (173–523 K) have been studied. Additionally spectroscopic properties viz., optical absorption and ESR spectra have been investigated. The optical absorption and ESR studies have revealed that vanadium ions do exist in both V⁴⁺ and V⁵⁺ states and the redox ratio is the highest in the glasses containing 0.8 mol% of V₂O₅. The results of conductivity measurements have indicated that there is a mixed conduction (both ionic and electronic). The ionic conduction seems to be dominant over polaron hopping only in the glasses containing V₂O₅ more than 0.8 mol% of V₂O₅. The impedance spectra have also indicated that the conduction is predominantly polaronic in nature. The frequency and temperature dependence of the electrical moduli as well as dielectric loss parameters have exhibited relaxation character attributed to the vanadyl complexes. The relaxation effects have been analyzed by the graphical method and from this analysis it has been established that there is a spreading of relaxation times. The results have been further discussed quantitatively in the light of different valance states of vanadium ions with the aid of the data on spectroscopic properties.     

Acoustic damping in Li2O–2B2O3 glass observed by inelastic X-ray and optical Brillouin scattering

The dynamic structure factor of lithium-diborate glass has been measured at several values of the momentum transfer Q using high resolution inelastic X-ray scattering. Much attention has been devoted to the low-Q-range, below the observed Ioffe–Regel crossover q_IR ≃ 2.1 nm⁻¹. We find that below q_IR, the linewidth of longitudinal acoustic waves increases with a high power of either Q, or of the frequency Ω, up to the crossover frequency Ω_IR ≃ 9 meV that nearly coincides with the center of the boson peak. This new finding strongly supports the view that resonance and hybridization of acoustic waves with a distribution of rather local low frequency modes forming the boson peak is responsible for the end of acoustic branches in strong covalent glasses. Further, we present high resolution Brillouin light-scattering data obtained at much lower frequencies on the same sample. These clearly rule out a simple Ω²-dependence of the acoustic damping over the entire frequency range.     

Influence of TiO2 on proton conductivity in fuel cell electrolytes based on sol–gel derived P2O5–SiO2 glasses

P₂O₅–TiO₂–SiO₂ based glasses have been prepared by a sol–gel process. The glasses were characterized by structural, thermal, nitrogen adsorption–desorption and conductivity measurements. The structural formation has been confirmed by the FTIR and NMR analysis. The proton conductivity of the glasses increased linearly with increase in temperature. Glasses with an average pore size less than 2 nm showed higher values of proton conductivity in humid atmosphere. The conductivity value increased from 6.47 × 10⁻⁴ S/cm to 3.04 × 10⁻² S/cm at 70% RH in the temperature range 30–90 °C. We observed in fuel cell measurements that the performance of the E1 electrode is superior to that of the other electrodes at the same operating condition. The power density shows a similar pattern to current density.