The influence of matrix mediated hopping conductivity, filler concentration, aspect ratio and orientation on the electrical response of carbon nanotube/polymer nanocomposites

A model to simulate the conductivity of carbon nanotube/polymer nanocomposites is presented. The proposed model is based on hopping between the fillers. A parameter related to the influence of the matrix in the overall composite conductivity is defined. It is demonstrated that increasing the aspect ratio of the fillers will increase the conductivity. Finally, it is demonstrated that the alignment of the filler rods parallel to the measurement direction results in higher conductivity values, in agreement with results from recent experimental work.

Effects of the environment on the electric conductivity of double-stranded DNA molecules

We present a theoretical analysis of the effects of the environment on charge transport in double-stranded synthetic poly(G)-poly(C) DNA molecules attached to two ideal leads. Coupling of the DNA to the environment results in two effects: (i) localization of carrier functions due to static disorder and (ii) phonon-induced scattering of the carriers between the localized states, resulting in hopping conductivity. A nonlinear Pauli master equation for populations of localized states is used to describe the hopping transport and calculate the electric current as a function of the applied bias. We demonstrate that, although the electronic gap in the density of states shrinks as the disorder increases, the voltage gap in the I-V characteristics becomes wider. A simple physical explanation of this effect is provided.

Quantum transport phenomena and shallow impurity states in CdSb

This work is dedicated to investigation of the energy spectrum of one of the most anisotropic narrow-gap semiconductors, CdSb. At the beginning of the present studies even the model of its energy band structure was not clear. Measurements of galvanomagnetic effects in wide temperature range (1.6 - 300 K) and in magnetic fields up to 30 T were chosen for clarifying of the energy spectrum in the intentionally undoped CdSb single crystals and doped with shallow impurities (In, Ag). Detection of the Shubnikov - de Haas oscillations allowed estimating the fundamental energy spectrum parameters. The shapes of the Fermi surfaces of electrons (sphere) and holes (ellipsoid), the number of the equivalent extremums for valence band (2) and their positions in the Brillouin zone were determined for the first time in this work. Also anisotropy coefficients, components of the tensor of effective masses of carriers, effective masses of density of states, nonparabolicity of the conduction and valence bands, g-factor and its anisotropy for n- and p-CdSb were estimated for the first time during these studies. All the results obtained are compared with the cyclotron resonance data and the corresponding theoretical calculations for p-CdSb. This is basic information for the analyses of the complex transport properties of CdSb and for working out the energy spectrum model of the shallow energy levels of defects and impurities in this semiconductor. It was found out existence of different mechanisms of hopping conductivity in the presence of metal - insulator transition induced by magnetic field in n- and p-CdSb. Quite unusual feature opened in CdSb is that different types of hopping conductivity may take place in the same crystal depending on temperature, magnetic field or even orientation of crystal in magnetic field. Transport properties of undoped p-CdSb samples show that the anisotropy of the resistivity in weak and strong magnetic fields is determined completely by the anisotropy of the effective mass of the holes. Temperature and magnetic field dependence of the Hall coefficient and magnetoresistance is attributed to presence of two groups of holes with different concentrations and mobilities. The analysis demonstrates that below Tcr ~ 20 K and down to ~ 6 - 7 K the low-mobile carriers are itinerant holes with energy E2 ≈ 6 meV. The high-mobile carriers, at all temperatures T < Tcr, are holes activated thermally from a deeper acceptor band to itinerant states of a shallower acceptor band with energy E1 ≈ 3 meV. Analysis of temperature dependences of mobilities confirms the existence of the heavy-hole band or a non-equivalent maximum and two equivalent maxima of the light-hole valence band. Galvanomagnetic effects in n-CdSb reveal the existence of two groups of carriers. These are the electrons of a single minimum in isotropic conduction band and the itinerant electrons of the narrow impurity band, having at low temperatures the energies above the bottom of the conduction band. It is found that above this impurity band exists second impurity band of only localized states and the energy of both impurity bands depend on temperature so that they sink into the band gap when temperature is increased. The bands are splitted by the spin, and in strong magnetic fields the energy difference between them decreases and redistribution of the electrons between the two impurity bands takes place. Mobility of the conduction band carriers demonstrates that scattering in n-CdSb at low temperatures is strongly anisotropic. This is because of domination from scattering on the neutral impurity centers and increasing of the contribution to mobility from scattering by acoustic phonons when temperature increases. Metallic conductivity in zero or weak magnetic field is changed to activated conductivity with increasing of magnetic field. This exhibits a metal-insulator transition (MIT) induced by the magnetic field due to shift of the Fermi level from the interval of extended states to that of the localized states of the electron spectrum near the edge of the conduction band. The Mott variablerange hopping conductivity is observed in the low- and high-field intervals on the insulating side of the MIT. The results yield information about the density of states, the localization radius of the resonant impurity band with completely localized states and about the donor band. In high magnetic fields this band is separated from the conduction band and lies below the resonant impurity bands.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

Magnetic and transport properties of LaMnO3+δ, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1-xSrxMn1-yFeyO3

Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

Evaluation of strontium-site-deficient Sr2Fe1.4Co0.1Mo0.5O6-δ-based perovskite oxides as intermediate temperature solid oxide fuel cell cathodes

In this paper strontium-site-deficient Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ-based perovskite oxides (S_xFCM) were prepared and evaluated as the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). All samples exhibited a cubic phase structure and the lattice shrinked with increasing the Sr-deficiency as shown in XRD patterns. XPS results determined that the transition elements (Co/Fe/Mo) in S_xFCM oxides were in a mixed valence state, demonstrating the small polaron hopping conductivity mechanism existed. Among the samples, S_1.950FCM presented the lowest coefficient of thermal expansion of 15.62 × 10^-6 K^-1, the highest conductivity value of 28 S cm^-1 at 500 °C, and the lowest interfacial polarization resistance of 0.093 Ω cm² at 800 °C, respectively. Furthermore, an anode-supported single cell with a S_1.950FCM cathode was prepared, demonstrating a maximum power density of 1.16 W cm^-2 at 800 °C by using wet H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that the introduction of Sr-deficiency can dramatically improve the electrochemical performance of Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ, showing great promise as a novel cathode candidate material for IT-SOFCs.

Hopping transport on a fractal: ac conductivity of porous silicon

We have measured the frequency dependence of the conductivity and the dielectric constant of various samples of porous Si in the regime 1 Hz-100 kHz at different temperatures. The conductivity data exhibit a strong frequency dependence. When normalized to the dc conductivity, our data obey a universal scaling law, with a well-defined crossover, in which the real part of the conductivity sigma' changes from an sqrt(omega) dependence to being proportional to omega. We explain this in terms of activated hopping in a fractal network. The low-frequency regime is governed by the fractal properties of porous Si, whereas the high-frequency dispersion comes from a broad distribution of activation energies. Calculations using the effective-medium approximation for activated hopping on a percolating lattice give fair agreement with the data.

Temperature dependence of the electrical conductivity of vapor grown carbon nanofiber/epoxy composites with different filler dispersion levels

The influence of the dispersion of vapor grown carbon nanofibers (VGCNF) on the electrical properties of VGCNF/epoxy composites has been studied. A homogeneous dispersion of the VGCNF does not imply better electrical properties. The presence of well distributed clusters appears to be a key factor for increasing composite conductivity. It is also shown that the main conduction mechanism has an ionic nature for concentrations below the percolation threshold, while above the percolation threshold it is dominated by hopping between the fillers. Finally, using the granular system theory it is possible to explain the origin of conduction at low temperatures.

Hopping conduction and persistent photoconductivity in Cu2ZnSnS4 thin films

The temperature dependence of electrical conductivity and the photoconductivity of polycrystalline Cu2ZnSnS4 were investigated. It was found that at high temperatures the electrical conductivity was dominated by band conduction and nearest-neighbour hopping. However, at lower temperatures, both Mott variable-range hopping (VRH) and Efros–Shklovskii VRH were observed. The analysis of electrical transport showed high doping levels and a large compensation ratio, demonstrating large degree of disorder in Cu2ZnSnS4. Photoconductivity studies showed the presence of a persistent photoconductivity effect with decay time increasing with temperature, due to the presence of random local potential fluctuations in the Cu2ZnSnS4 thin film. These random local potential fluctuations cannot be attributed to grain boundaries but to the large disorder in Cu2ZnSnS4.

Dielectric and Conductivity Studies on Cobalt Phthalocyanine Tetramers

Electrically conductive organic and metalloorganic polymers are of great interest and they have applications in electronic, optical, photonic, photoelectric, electrochemical, and dielectric devices. Tetrameric cobalt phthalocyanine was prepared by conventional chemical method. The dielectric permittivity of the tetrameric cobalt phthalocyanine sample was evaluated from the observed capacitance values in the frequency range 100 KHz to 5 MHz and in the temperature range of 300 to 383°K. It is found that the system obeys the Maxwell Wagner relaxation of space charge phenomenon. Further, from the permittivity studies AC conductivity was evaluated. The values of AC conductivity and DC conductivity were compared. Activation energy was calculated. To understand the conduction mechanism Mott’s variable range hopping model was applied to the system. The T 1/4 behavior of the DC conductivity along with the values of Mott’s Temperature (T0), density of states at the Fermi energy N (EF), and range of hopping R and hopping energy W indicate that the transport of charge carriers are by three-dimensional variable range hopping

Composition Dependent Study of AC conductivity in AsSe samples

The room temperature AC conductivity σ(ω) of amorphous AsSe samples with various compositions have been measured in the 103 -106 Hz frequency range. The results indicate that ac conductivity is proportional to n with n=0.89±.01 in the 103 –106 Hz frequency range. Consideration of different models for the frequency –dependent conductivity leads to thermally activated hopping as the most likely process

Ionized oxygen vacancy-related electrical conductivity in (Pb(1-x)La(x)) (Zr(0.90)Ti(0.10))(1-x/4)O(3) ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

ac conductivity and conduction mechanism of NaNbO3 semiconductor antiferroelectric ceramic: A relaxational approach at high temperature

The electric properties of the sodium niobate perovskite ceramic were investigated by impedance spectroscopy in the frequency range from 5 Hz to 13 MHz and from room temperature up to 1073 K, in a thermal cycle. Both capacitance and conductivity exhibit an anomaly at around 600 K as a function of the temperature and frequency. The electric conductivity as a function of angular frequency sigma(omega) follows the relation sigma(omega)=Aomega(s). The values of the exponent s lie in the range 0.15less than or equal tosless than or equal to0.44. These results were discussed considering the conduction mechanism as being a type of polaron hopping. (C) 2003 American Institute of Physics.

Insulator-to-metal transition in vanadium supersaturated silicon: variable-range hopping and Kondo effect signatures

We report the observation of the insulator-to-metal transition in crystalline silicon samples supersaturated with vanadium. Ion implantation followed by pulsed laser melting and rapid resolidification produce high quality single-crystalline silicon samples with vanadium concentrations that exceed equilibrium values in more than 5 orders of magnitude. Temperature-dependent analysis of the conductivity and Hall mobility values for temperatures from 10K to 300K indicate that a transition from an insulating to a metallic phase is obtained at a vanadium concentration between 1.1 × 10^(20) and 1.3 × 10^(21) cm^(−3) . Samples in the insulating phase present a variable-range hopping transport mechanism with a Coulomb gap at the Fermi energy level. Electron wave function localization length increases from 61 to 82 nm as the vanadium concentration increases in the films, supporting the theory of impurity band merging from delocalization of levels states. On the metallic phase, electronic transport present a dispersion mechanism related with the Kondo effect, suggesting the presence of local magnetic moments in the vanadium supersaturated silicon material.

Procesos hopping a través del modelo difusional en materiales nanocristalinos usados para aplicaciones fotovoltaicas

Se presentan los modelos de hopping de rango variable (variable range hopping; VRH), vecinos cercanos (nearest neighbor hopping; NNH) y barreras de potencial presentes en las fronteras de grano; como mecanismos de transporte eléctrico predominantes en los materiales semiconductores para aplicaciones fotovoltaicas. Las medidas de conductividad a oscuras en función de temperatura fueron realizadas para región de bajas temperaturas entre 120 y 400 K con Si y compuestos Cu3BiS2 y Cu2ZnSnSe4. Siguiendo la teoría de percolación, se obtuvieron parámetros hopping y la densidad de estados cerca del nivel de Fermi, N(EF), para todas las muestras. A partir de los planteamientos dados por Mott para VRH, se presentó el modelo difusional, que permitió establecer la relación entre la conductividad y la densidad de estados de defecto o estados localizados en el gap del material. El análisis comparativo entre modelos, evidenció, que es posible obtener mejora hasta de un orden de magnitud en valores para cada uno de los parámetros hopping que caracterizan el material.