Tunneling conductivity in lithiated transition metal oxide cathode Li<Subscript>0.9</Subscript>[Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>]O<Subscript>1.95</Subscript>

Electrical complex ac conductivity of the compound Li_0.9[Ni_1/3Mn_1/3Co_1/3]O_1.95 has been studied in the frequency range 10 Hz–2 MHz and in the temperature range 93–373 K. It has been observed that the frequency dependence of the ac conductivity obeys a power law and the temperature dependence of the ac conductivity is quite weak. The experimental data have been analyzed in the framework of several theoretical models based on quantum mechanical tunneling and classical hopping over barriers. It has been observed that the electron tunneling is dominant in the temperature range from 93 K to 193 K. A crossover of relaxation mechanism from electron tunneling to polaron tunneling is observed at 193 K. Out of the several models discussed, the electron tunneling and the polaron tunneling models are quite consistent with the experimental data for the complex ac conductivity. The various parameters obtained from the fits of the experimental results for the real and imaginary parts of the conductivity to the predictions of these models are quite reasonable.     

Thermal conductivity and magnetic properties of the B substituted Ca3Co4O9

In this study, we reported the effects of the boron (B) substitution into the Ca site in the Ca₃Co₄O₉ system on the electrical, thermal and magnetic properties between 300 K and 5 K. The results indicated that the B-substitution into the system caused an increase of resistivity due to the decrease on carrier concentration. Thermal conductivity decreased for the x = 0.5 B-substituted sample and then increased with increasing the B-content. Analysis on the thermal conductivity of samples showed that the phonon–phonon interaction term is the dominant component in the total thermal conductivity for all the samples. It was found that the point defect contribution to the thermal conductivity increased by increasing the B-content. The temperature dependence of magnetic susceptibility showed a paramagnetic behavior at room temperature and ferrimagnetic behavior below 20 K for unsubstituted sample. But, the magnetization decreased in the B-substituted samples. The substitution of B into the Ca site destroyed the interlayer coupling, which resulted in the decrease of the ferromagnetic behavior. The susceptibility data was fitted using Curie–Weiss law with temperature independent term and the μ_eff values were calculated to be 1.42 μ_B and 3.89 μ_B for unsubstituted sample and the highest B-substitution, respectively.     

Spectral broadening and electron–photon coupling in III–V infrared detectors of low dimensional quantum confined system

Present work explores the mid-IR photodetection mechanism in III–V quantum confined system in twofold ways. Firstly, it models the extent of spectral linewidth broadening of photo-detector. Secondly, it investigates whether a strong perturbation of light can modulate the electronic bandstructure. Photo-absorption mechanism in the detector correlated to reduced carrier lifetime in ground state leading to homogeneous spectral widening is calculated. Besides, contribution of non-uniform size and composition of quantum dots towards spectral broadening is modeled in order to get the envelop of inhomogeneously broadened photocurrent spectrum. Our model generates photocurrent spectrum with 1.4 μm broadening centered at 3.5 μm at 77 K for a DWELL-IP, which agrees with the experimental result. The calculated photocurrent spectral width of 1.3 μm for GaAs/AlGaAs Quantum Well (QW) centered at 8.31 μm at 77 K also supports experimental data. In addition, our calculation reveals the emergence of a broad resonant peak in the spectrum of QW-IP in far infrared region (20–50 μm) as the photon volume density increases up to 0.1% of carrier density inside the active region. We introduce a hybrid density-of-states for strongly coupled electron–photon system to explain both mid and far IR peak.     

On the room temperature multiferroic BiFeO<Subscript>3</Subscript>: magnetic,dielectric and thermal properties

Magnetic dc susceptibility between 1.5 and 800 K, ac susceptibility and magnetization, thermodynamic properties, temperature dependence of radio and audio-wave dielectric constants and conductivity, contact-free dielectric constants at mm-wavelengths, as well as ferroelectric polarization are reported for single crystalline BiFeO₃. A well developed anomaly in the magnetic susceptibility signals the onset of antiferromagnetic order close to 635 K. Beside this anomaly no further indications of phase or glass transitions are indicated in the magnetic dc and ac susceptibilities down to the lowest temperatures. The heat capacity has been measured from 2 K up to room temperature and significant contributions from magnon excitations have been detected. From the low-temperature heat capacity an anisotropy gap of the magnon modes of the order of 6 meV has been determined. The dielectric constants measured in standard two-point configuration are dominated by Maxwell-Wagner like effects for temperatures T > 300 K and frequencies below 1 MHz. At lower temperatures the temperature dependence of the dielectric constant and loss reveals no anomalies outside the experimental errors, indicating neither phase transitions nor strong spin phonon coupling. The temperature dependence of the dielectric constant was measured contact free at microwave frequencies. At room temperature the dielectric constant has an intrinsic value of 53. The loss is substantial and strongly frequency dependent indicating the predominance of hopping conductivity. Finally, in small thin samples we were able to measure the ferroelectric polarization between 10 and 200 K. The saturation polarization is of the order of 40 μC/cm², comparable to reports in literature.     

Hopping and tunneling transport over a wide temperature range in chemically synthesized doped and undoped polypyrrole

Polypyrrole was synthesized by the chemical oxidation method in the presence of phosphoric acid by varying oxidant to monomer molar ratio for the optimization of electrical conductivity. The conductivity in doped polypyrrole reached up to a maximum value of 9.18 S/cm. Granular morphology was observed in chemically synthesized polypyrrole. Neutralization of doped polypyrrole was done with aqueous ammonium hydroxide and three orders of reduced conductivity were obtained in neutral polypyrrole. Doped and undoped samples of polypyrrole were then electrically characterized over a wide temperature range of 10–300 K. The measured electrical conductivity rises with the increase in temperature and shows the semiconducting nature of the material. Strong and weak temperature dependence of conductivity was revealed by undoped and doped polypyrrole samples respectively. An effort has been made to explore the electrical transport in doped and undoped polypyrrole by charge transport models. The experimental data obeys Kivelson’s hopping model in temperature range of 60–300 K and fluctuation assisted tunneling was the dominant conduction mechanism below 60 K.     

Theoretical investigation of structural and thermo-mechanical properties of thoria

We investigated the thermo-mechanical properties of thoria. Thoria is considered to be a candidate for a new safer nuclear fuel due to its higher thermal conductivity and because, unlike urania, it does not degrade in an oxidizing atmosphere. Thoria is also of interest since, like other metal oxides, it has high dielectric constant. Here we analyze thoria's thermo-mechanical properties using the ab initio method. We demonstrate that first principles calculations are valuable in complementing the limited experimental data available for thoria. The lambda phase transition is determined to be at higher temperature than in urania, where transition is observed at 2670 K, and therefore, in contrast to urania, we found that in thoria both atoms (Th and O) are confined at 2700 K.     

Dielectric relaxation and ac conductivity behavior of carboxyl functionalized multiwalled carbon nanotubes/poly (vinyl alcohol) composites

We study the dielectric relaxation and ac conductivity behavior of MWCNT-COOH/Polyvinyl alcohol nanocomposite films in the temperature (T) range 303–423 K and in the frequency (f) range 0.1 Hz–1 MHz. The dielectric constant increases with an increase in temperature and also with an increase in MWCNT-COOH loading into the polymer matrix, as a result of interfacial polarization. The permittivity data were found to fit well with the modified Cole-Cole equation. Temperature dependent values of the relaxation times, free charge carrier conductivity and space charge carrier conductivity were extracted from the equation. An observed increment in the ac conductivity for the nanocomposites was analysed by a Jonscher power law which suggests that the correlated barrier hopping is the dominant charge transport mechanism for the nanocomposite films. The electric modulus study revealed deviations from ideal Debye-type behavior which are explained by considering a generalized susceptibility function. XRD and DSC results show an increase in the degree of crystallinity.     

Conductivity spectra and ion dynamics of a salt-in-polymer electrolyte

We present, for the first time, broadband conductivity spectra of a salt-in-polymer electrolyte, i.e., of 1 molal NaPF₆ dissolved into a crosslinked PEO-PPO random copolymer. The experimental frequency range spans nearly 12 decades, extending up to the far infrared. The temperature range is from 303 K to 363 K. The conductivity spectra show a remarkably gradual onset of the dispersion, which is reminiscent of ion conducting glasses and crystalline ion conductors, where ions hop via well-defined sites. On the other hand, the DC conductivity of the polymer electrolyte shows a non-Arrhenius temperature dependence, thus resembling dynamically coupled systems such as supercooled melts. Any approach to understanding these seemingly contradictory features must include ion–ion interactions and, hence, go beyond models based on free volume theory. Such an approach is provided by the MIGRATION concept (MIsmatch Generated Relaxation for the Accommodation and Transport of IONs). In this treatment, the non-Arrhenius DC conductivity is described by an equation which yields, e.g., the elementary hopping rate and the shape of the conductivity spectra at higher frequencies. The entire conductivity spectra with the vibrational component suitably removed is a superposition of two components—one due to ionic displacements resulting in translational motion, the other due to localized movements causing a Nearly Constant Loss (NCL) type behaviour.     

Quantum dissociation of a vortex-antivortex pair in a long josephson junction

The thermal and the quantum dissociation of a single vortex-antivortex (VAV) pair in an annular Josephson junction is experimentally observed and theoretically analyzed. In our experiments, the VAV pair is confined in a pinning potential controlled by external magnetic field and bias current. The dissociation of the pinned VAV pair manifests itself in a switching of the Josephson junction from the superconducting to the resistive state. The observed temperature and field dependence of the switching current distribution is in agreement with the analysis. The crossover from the thermal to the macroscopic quantum tunneling mechanism of dissociation occurs at a temperature of about 100 mK. We also predict the specific magnetic field dependence of the oscillatory energy levels of the pinned VAV state.     

Thermally induced effects on structural and electrical properties of selenium-rich Cd-Se thin films

The effect of annealing in nitrogen atmosphere on structural and electrical properties of selenium rich CdSe (SR-CdSe) thin films deposited by thermal evaporation onto glass substrates were studied. X-ray diffraction (XRD) patterns showed that the as-prepared films were amorphous, whereas the annealed films were polycrystalline. Analyzing XRD patterns reveals the coexistence of both Se and CdSe crystalline phases which exhibits a hexagonal structure. The microstructure parameters (crystallite size, microstrain and dislocation density) were calculated for annealed films.Temperature dependence (300–500 K) of d.c. conductivity was studied for as-prepared and annealed thin films. The experimental results indicate that the electrical conduction taking place through thermally activated process. At higher temperatures, electrical conduction for as-prepared film is taking place in the extended states while localized states conduction in the band tails is most likely to take place for annealed films. Regarding the lower temperature range, conduction by hopping in the localized states near the Fermi level is found to be dominant. Thus, conductivity data in this range was analyzed using Mott's variable range hopping conduction, where Mott's parameters were calculated for SR-CdSe thin films.     

Calculation of thermophysical properties for CO2 gas using an ab initio potential model

The density, isochoric heat capacity, shear viscosity and thermal conductivity of CO₂ gas in the pressure range of 1–50 atm and 300 K are calculated based on a five-centre potential model obtained from ab initio calculations of the intermolecular potential of a CO₂ dimer. The quantum effects of the intramolecular motion are included in a model by the Monte Carlo (MC) Method. Without using any experimental data, the present model achieves excellent agreements between the calculated thermophysical properties and experimental data for all simulated CO₂ densities except the highest one at 135 kg/m³ (3 mol/L). The contributions of potential to the thermophysical properties of the moderate dense CO₂ gas and their dependence on density are investigated in detail.     

Well-width dependence of interface roughness scattering in GaAs/Ga1 − xAlxAs quantum wells

Well-width dependence of quantum and transport mobilities of electrons in GaAs/GaAlAs multiple quantum wells is studied for wells with widths ranging between 50 Å and 145 Å Experimental results are obtained from the amplitude analysis of the Shubnikov–de Haas (SdH) oscillations and from conventional Hall measurements at temperatures betweenT = 15 K and 4.2 K. A novel technique is employed to estimate, theoretically, the interface roughness parameters from electron quantum and transport lifetimes. The modelling is carried out for a range of layer fluctuations, width (Δ) and lateral size (Λ), as to obtain the best fit to the experimental results for individual samples. Our results indicate that the interface roughness scattering limits equal both quantum and transport mobilities at low temperatures, and that the nature of scattering by interface roughness (small or large angle) depends not only on the size and the width of the fluctuations but also on the distribution of these fluctuations within the samples. Therefore, unlike the predictions of the existing theoretical models, which assume constant values of Δ and Λ for all well widths, the well-width dependence of interface roughness scattering cannot be verified experimentally.     

Sodium diffusion in cryolite at elevated temperatures studied by quasielastic neutron scattering

Quasielastic neutron scattering (QENS) has been applied to study the sodium mobility on nanosecond time scales in the perovskite fluoride cryolite, Na₃AlF₆, at high temperatures. Up to T = 1153 K the diffusion of Na ions is well described by a diffusion process of jumps between six and eight-fold coordinated sites. Above this temperature, where a step-like increase in the electrical conductivity occurs, the jump length increases, which indicates additional jumps over larger distances. The electrical conductivity derived from the self-diffusion coefficient via the Nernst–Einstein relation and the corresponding activation energy are in excellent agreement with the previous conductivity measurements. We conclude that the jump diffusion of sodium ions is the dominant mechanism for the electrical conductivity in cryolite at high temperatures up to T = 1153 K.     

The thermodynamic properties of normal liquid helium 3

The thermodynamic properties of normal liquid helium 3 are calculated by using the lowest order constrained variational (LOCV) method. The Landau Fermi liquid model and Fermi-Dirac distribution function are considered as our statistical model for the uncorrelated quantum fluid picture and the Lennard-Jones and Aziz potentials are used in our truncated cluster expansion (LOCV) to calculate the correlated energy. The single particle energy is treated variationally through an effective mass. The free energy, pressure, entropy, chemical potential and liquid phase diagram as well as the helium 3 specific heat are evaluated, discussed and compared with the corresponding available experimental data. It is found that the critical temperature for the existence of the pure gas phase is about 4.90 K (4.45 K), which is higher than the experimental prediction of 3.3 K, and the helium 3 flashing temperature is around 0.61 K (0.50 K) for the Lennard-Jones (Aziz) potential.     

Γ to Xzelectron transfer times in type-II GaAs/AlAs superlattices due to emission of confined and interface phonons

We calculate the Γ →  X_zelectron transfer times due to the emission of confined and interface LO phonons in type-II GaAs–AlAs and AlGaAs–AlAs superlattices. A dielectric continuum model is employed to describe the electron–phonon interaction, and the electron envelope wavefunctions are obtained from a Kronig–Penney model. The calculated transfer times are in good agreement with available experimental results. We have used two different sets of AlAs X-valley effective masses obtained from different experiments and we show that the transfer times calculated with the heavier masses are in closer agreement with the measured data.     

Experimental study of thermal conductivity of refrigerant R-409A in vapor phase

Thermal conductivity of refrigerant R-409A in vapor phase was studied in the range of temperatures 306–425 K and pressures 0.12–1.33 MPa. Measurements were performed with the stationary method of coaxial cylinders. Uncertainty of experimental data on thermal conductivity was 1.5–2.5 %, and errors of temperature and pressure measurements did not exceed 0.05 K and 4 kPa, respectively. Approximating dependence of thermal conductivity on pressure and temperature was obtained. Thermal conductivity on dew line and in ideal gas state was calculated.     

Comparison of quantum,semi-classical and classical methods in the calculation of nitrogen self-broadened linewidths

We perform dynamical calculations on two robust N₂–N₂ potential energy surfaces in order to intercompare pressure broadening coefficients derived from close coupling and coupled states quantum dynamical methods, the semi-classical model of Robert and Bonamy and a full classical method. The coupled states and full classical results compare well with the experimental results or with close coupling values when available. This study confirms that the classical method is a good alternative at room and high temperatures to quantum dynamical methods. The results obtained using the semi-classical method however deviate from the other sets of data at all temperatures considered here (77–2400 K).     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Electrical transport properties of consolidated ZnSe quantum dots at and above room temperature

Here we report a comprehensive study on the prevailing conduction mechanism and dielectric relaxation behavior of consolidated Zinc Selenide quantum dots in the frequency range of 1 kHz ≤ f ≤ 1.5 MHz and in the temperature range of 298K ≤ T ≤ 573 K. The ac conductivity increases either with increase in temperature or with increase in frequency, which is explained by the Jonscher Power law. At higher temperatures, correlated barrier hopping is found to be the prevalent charge transport mechanism with a maximum barrier height of 0.88 eV. The dielectric constant of the sample is found to exhibit weak temperature dependence. DC conductivity study reveals the semiconducting nature of the sample and it is discussed in the light of polaron hopping conduction. From the impedance spectroscopic study, role of the grains and grain boundaries in the overall electrical transport properties have been elucidated by considering an electrical equivalent circuit (composed of resistances and constant phase elements). Electric modulus study reveals non-Debye responses of the sample in the experimental range.     

Sliding-induced decoupling and charge transfer between the coexisting Q1 and Q2 charge density waves in NbSe3

Using high-resolution x-ray scattering in the presence of an applied current, we report evidence for a dynamical decoupling between the two NbSe3 charge-density waves (CDWs), Q1 (T(C1)=145 K) and Q2 (T(C2)=59 K), coexisting below T(C2). Simultaneous and oppositely directed shifts of the relevant CDW superlattice spots develop above a threshold current which we identify as the depinning threshold I(C1) for the more strongly pinned upper CDW Q1 (I(C1) approximately 10I(C2)). In contrast with shifts induced by current conversion processes, the present effect is not current polarized and is not limited to the current-contact regions. We propose a model which explains this instability through a sliding-induced charge transfer between the two electronic reservoirs corresponding to the Q1 and Q2 CDWs.