Transport properties and conduction mechanisms in CuFe2O4 and Cu1−xZnxGa0.3Fe1.7O4 compounds

Single-phase structure of CuFe₂O₄ and Cu_1−xZn_xGa_0.3Fe_1.7O₄; with (0.0≤x≤0.5) are synthesized. Electrical conductivity measurements as a function of temperature are carried out in the frequency range (10²-10⁵ Hz) for the prepared samples. The obtained results of these materials reveal a metallic-like behavior in the low range of frequency. At high frequency regime metallic-to-semiconductor transition has been observed as the compositional parameter x increases. Metallic-like behavior is accompanied with samples having low Zn content, where cation-cation [Cu-Cu] interaction is major at the octahedral B-sites and semiconductor behavior is associated with compounds having high Zn content, where cation-anion-cation [Fe-O-Fe] interaction is most predominant at B-sites in these spinel oxides. All studied compositions exhibit a transition with change in the slope of conductivity versus temperature curve. This transition temperature is found to decrease linearly with increasing Zn concentration x. The relation of the universal exponent s with temperature indicates the presence of two hopping conduction mechanisms; the correlated barrier hopping CBH at low Zn content x≤0.2 and small polaron (SP) at Zn content x≥0.3.     

Effect of substitution of K ions on the structural and electrical properties of nanocrystalline MgAl2O4 spinel oxide

Potassium substituted nanosized magnesium aluminates having a nominal composition Mg_1−xK_xAl₂O₄ where x=0.0, 0.25, 0.5, 0.75, 1.0 have been synthesized by the chemical co-precipitation method. The samples have been characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), and dc electrical resistivity measurements. The XRD results reveal that the samples are spinel single phase cubic close packed crystalline materials. The calculated crystallite size ranges between 6 and 8 nm. The behaviour of the lattice constant seems to deviate from the Vegard's law. While X-ray density clearly increases, the bulk density and consequently, the percentage porosity do not exhibit a significant change on increasing the K⁺ content. The SEM micrographs suggest homogeneous distribution of the nanocrystallites in the samples. The dc electrical resistivity exhibits a typical semiconducting behaviour. Substitution of a Mg²⁺ ion by a K⁺ ion provides an extra hole to the system, which forms small polaron. Thermally activated hopping of these small polarons is believed to be the conduction mechanism in the Mg_1−xK_xAl₂O₄. The activation energy of hopping of small polarons has been calculated and found K⁺ ions content dependent.     

Structural,magnetic and electrical properties of Co1−xZnxFe2O4 synthesized by co-precipitation method

Nanoparticles of Co_1−xZn_xFe₂O₄ with stoichiometric proportion (x) varying from 0.0 to 0.6 were prepared by the chemical co-precipitation method. The samples were sintered at 600 °C for 2 h and were characterized by X-ray diffraction (XRD), low field AC magnetic susceptibility, DC electrical resistivity and dielectric constant measurements. From the analysis of XRD patterns, the nanocrystalline ferrite had been obtained at pH=12.5–13 and reaction time of 45 min. The particle size was calculated from the most intense peak (3 1 1) using the Scherrer formula. The size of precipitated particles lies within the range 12–16 nm, obtained at reaction temperature of 70 °C. The Curie temperature was obtained from AC magnetic susceptibility measurements in the range 77–850 K. It is observed that Curie temperature decreases with the increase of Zn concentration. DC electrical resistivity measurements were carried out by two-probe method from 370 to 580 K. Temperature-dependent DC electrical resistivity decreases with increase in temperature ensuring the semiconductor nature of the samples. DC electrical resistivity results are discussed in terms of polaron hopping model. Activation energy calculated from the DC electrical resistivity versus temperature for all the samples ranges from 0.658 to 0.849 eV. The drift mobility increases by increasing temperature due to decrease in DC electrical resisitivity. The dielectric constants are studied as a function of frequency in the range 100 Hz–1 MHz at room temperature. The dielectric constant decreases with increasing frequency for all the samples and follow the Maxwell–Wagner's interfacial polarization.     

Small polaron electron transport in reduced CeO2 single crystals

An investigation of the electrical properties of reduced ceria, CeO_2?x, carried out on single crystals, shows that CeO_2?x provides one of the clearest examples of hopping conduction and the small polaron mechanism. Included are conductivity and Seebeck coefficient measurements at constant x, obtained by sealing off the specimen chamber after reduction. The Seebeck coefficient is independent of temperature, suggesting that the number of carriers is constant. On the other hand, the mobility is activated, with activation energy E_h = 0.40 eV at small x and increasing to 0.52 eV at x = 0.25. The results for the mobility preexponential are consistent with the adiabatic theory of small polaron behavior. A puzzling feature of the Seebeck data as a function of x is that, for low x, the data fit the well-known Heikes formula, without a degeneracy factor of 2 for spin. Nevertheless, these data are interpreted to show that the proportion of mobile carriers decreases as x increases, presumably because of the presence of short-range ordered configurations which immobilize some carriers.     

Effect of fabrication parameters on the electrical conductivity of YxSr1−xTiO3 for anode materials

Yttrium-doped strontium titanate (Y_xSr_1−xTiO₃), as probable anode material for SOFC, was prepared by solid-state reaction. The solubility of yttrium in SrTiO₃ at different temperatures was examined and the electrical conductivities of Y_xSr_1−xTiO₃ were measured from 500 to 1000 °C. The effects of doping amount, fabrication atmosphere, and sintering temperature on the electrical conductivity of Y_xSr_1−xTiO₃ were investigated. Y_xSr_1−xTiO₃ with x=0.08 was found to give the maximum electrical conductivity, 71 S/cm at 800 °C in pure hydrogen. Reducing atmospheres and appropriate sintering temperatures play a positive role in improving the electrical conductivity.     

Transport coefficients and defect structure of Sb2−xAgxTe3 single crystals

Incorporation of Ag in the crystal lattice of Sb₂Te₃ creates structural defects that have a strong influence on the transport properties. Single crystals of Sb_2−xAg_xTe₃ (x=0.0; 0.014; 0.018 and 0.022) were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 5-300 K. With an increasing content of Ag the electrical resistance, the Hall coefficient and the Seebeck coefficient all decrease. This implies that the incorporation of Ag atoms in the Sb₂Te₃ crystal structure results in an increasing concentration of holes. However, the doping efficiency of Ag appears to be only about 50% of the expected value. We explain this discrepancy by a model based on the interaction of Ag impurity with the native defects in the Sb_2−xAg_xTe₃ crystal lattice. Defects have a particularly strong influence on the thermal conductivity. We analyze the temperature dependence of the lattice thermal conductivity in the context of the Debye model. Of the various phonon scattering contributions, the dominant influence of Ag incorporation in the crystal lattice of Sb₂Te₃ is revealed to be point-defect scattering where both the mass defect and elastic strain play a pivotal role.     

Magnetic and electrical properties of new magnetic phase in Si1−xMnx crystals

We have investigated the magnetic and electrical transport properties of Si_1−xMn_x single crystals grown by the vertical Bridgman method. The alloys with Mn concentrations up to x=0.64 have weak ferromagnetic ordering around T_C∼30 K. However, Si_0.25Mn_0.75 alloys show weak ferromagnetic ordering at 70 K and antiferromagnetic ordering at 104 K, which is confirmed by magnetization and electrical transport studies.     

On the coexistence of spin and lattice polarons in the La0.67−xEuxCa0.33MnO3 CMR system

The electrical and magnetic transport properties of the La_0.67−xEu_xCa_0.33MnO₃ system exhibit lowering of insulator to metal and paramagnetic to ferromagnetic transition temperature (T_C) with the increase of Eu concentration in addition to possessing CMR property. The temperature variation of electrical resistivity and magnetic susceptibility for x=0.21 is found to have two distinct regions in the paramagnetic state for T>T_P; one with the localization of lattice polaron in the high-temperature region (T>1.5T_P) satisfying the dynamics of variable range hopping (VRH) model and the other being the combination of the spin and lattice polarons in the region T_P<T<1.5T_P. The resistivity variation with temperature and magnetic field, the cusp in the resistivity peak and CMR phenomenon are interpreted in terms of coexistence of spin and lattice small polarons in the intermediate region (T_P<T<1.5T_P). The spin polaron energy in the La_0.46Eu_0.21Ca_0.33MnO₃ system is estimated to be 106.73±0.90 meV and this energy decreases with the increase of external magnetic field. The MR ratio is maximal with a value of 99.99% around the transition temperature and this maximum persists till T→0 K, at the field of 8 T.     

Thermal, electrical, and electrochemical properties of Lanthanum-doped Ba0.5Sr0.5 Co0.8Fe0.2O3-δ

Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba_0.5Sr_0.5)_1-xLa_xCo_0.8Fe_0.2O_3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba_0.5Sr_0.5 Co_0.8Fe_0.2O_3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm⁻¹ at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm², which was only 46% of BSCF.     

Non-adiabatic polaron hopping conduction in CaMn1−xCrxO3 (0?x?0.3)

DC electrical conductivity (σ_dc) of electron-doped antiferromagnetic CaMn_1−xCr_xO₃ (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σ_dc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr³⁺ has larger ionic size compared to that of Mn⁴⁺. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO₃ manganites.     

Oxygen vacancy doping effect on the electrical and magnetic behavior of Ba5−xLaxNb4−xTixO15

We report electric and magnetic properties of oxygen deficient Ba_5−xLa_xNb_4−xTi_xO_15−δ phases, which have been prepared by solid-state reaction method followed by a controlled reduction process under hydrogen atmosphere. The extra electrons added by the formation of the oxygen vacancies (δ) introduce localized spins and the magnetic susceptibility can be described by a temperature-independent contribution and a Curie-Weiss term associated to the Ti³⁺ ion formation. Besides, the experimental resistivity (ρ) data of these four reduced compounds are well described in a wide temperature range with the equation , which suggests the presence of small polarons in the system. Although, all samples present electrical insulating behavior, the electrical resistivity decreases four orders of magnitude for intermediate x values. We interpreted this fact as a consequence of the mix between the localized bands of the Nb and Ti ions, which favors the promotion of carriers due to reduction of the band gap.     

Structural, chemical and magnetic investigations of polycrystalline Zn1−xMnxO

Present study reports the detailed structural and magnetic, as well as chemical analysis of polycrystalline Zn_1−xMn_xO (where x=0, 0.005, 0.01, 0.03, 0.05 and 0.1) samples synthesized by the high-temperature solid state reaction route. X-ray diffraction studies reveal the presence of secondary phase for higher Mn-doping concentrations (x≥0.03). Secondary phase formation having spinel structure is confirmed and reported as an evidence for the first time using transmission electron microscopy study. Chemical investigations using X-ray photoelectron spectroscopy showed the presence of Mn in two valence states. From the observed results we are of the opinion that Zn²⁺ ions, mainly present at or near grain boundaries, diffuse into manganese oxide to form a stable spinel phase Zn_xMn_3−xO₄ at or near the grain boundaries of ZnO/Zn_1−xMn_xO. Magnetization measurements did not show any magnetic transition down to 5 K.     

Magnetic properties and specific heat of Dy1−xLaxNi2 compounds

Magnetic and specific heat measurements have been carried out on polycrystalline series of single-phase Dy_1−xLa_xNi₂ (0?x?1) solid solutions. The compounds have a Laves-phase superstructure (space group F4¯3m) with the lattice parameter gradually increasing with decreasing Dy content. The samples with x?0.8 are ferromagnetic with the Curie temperature below 22 K. At high temperatures, all solid solutions are Curie-Weiss paramagnets. The Debye temperature, phonon and conduction electron contributions as well as a magnetic contribution to the heat capacity have been determined from specific heat measurements. The magnetocaloric effect was estimated from specific heat measurements performed in a magnetic field of 0.42 and 4.2 T.     

Characterization and electrical properties of V2O5-CuO-P2O5 glasses

Characterization and electrical properties of vanadium-copper-phosphate glasses of compositions xV₂O₅-(40−x)CuO-60P₂O₅ have been reported. X-ray diffraction (XRD) confirms the amorphous nature of these glasses. It was observed that, the density (d) decreases gradually while the molar volume (V_m) increases with the increase of the vanadium oxide content in such glasses. This may be due to the effect of the polarizing power strength, PPS, which is a measure of ratio of the cation valance to its diameter. The dc conductivity increases while the activation energy decreases with the increase of the V₂O₅ content. The dc conductivity in the present glasses is electronic and depends strongly upon the average distance, R, between the vanadium ions. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron.     

Defect formation and transport in mixed-conducting La0.90Sr0.10Al0.85−xFexMg0.15O3−δ

The redox behavior of perovskite-type La_0.90Sr_0.10Al_0.85−xFe_xMg_0.15O_3−δ (x=0.20-0.40) mixed conductors was analyzed by the Mössbauer spectroscopy and measurements of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10⁻²⁰ to 0.5 atm at 1023-1223 K. The results combined with oxygen-ion transference numbers determined by the faradaic efficiency technique in air, were used to calculate defect concentrations, mobilities, and partial ionic and p- and n-type electronic conductivities as a function of oxygen pressure. The redox and transport processes can be adequately described in terms of oxygen intercalation and iron disproportionation reactions, with the thermodynamic functions independent of defect concentrations. No essential delocalization of the electronic charge carriers was found. The oxygen non-stoichiometry values estimated from the conductivity vs. p(O₂) dependencies, coincide with those evaluated from the Mössbauer spectra.     

DC and AC conductivities of (As2S3)100−x(AsSe0.5Te0.5I)x chalcogenide glasses

The DC and AC conductivities of samples from the system (As₂S₃)_100−x(AsSe_0.5Te_0.5I)_x, where x=0, 5, 10, 15, 20, 25, 30, 35, 50, 70 and 90 mol%, were measured as a function of temperature. Besides, the AC conductivities of the samples with x=10 and 30 were measured as a function of frequency from room temperature to the glass transition temperature. The DC conductivity dependence on temperature is of the Arrhenius type, whereas the value of the pre-exponential factor suggests the electrical conduction by localized states in the band tails and by localized states near the Fermi level. The small values of the conduction activation energy (10⁻²-10⁻¹ eV) obtained at higher frequencies suggest that the conduction in these materials is due to hopping of charge carriers between close defect states near the Fermi level.     

Small polaron migration in LixMn2O4: From first principles calculations

Migration of small polarons in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ is studied via first principles calculations. Migration energy barriers of single small polaron migrations in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ are 0.22 eV, 0.45 eV and 0.35 eV, respectively. The energy level changes of Mn-3d states along the polaron migration path are analyzed in detail. Results indicate that the activation energy barrier of polaron migration is strongly associated with the energy level shift of Mn-3dz² orbital, which is dependent on the short range structural arrangement of Mn³⁺/Mn⁴⁺ in the crystal. The electrical conduction properties of Li_xMn₂O₄ at room temperature are then discussed.     

Structural characterization and magnetization of Mg0.7Zn0.3SmxFe2−xO4 ferrites

Mg_0.7Zn_0.3Sm_xFe_2−xO₄ ferrites were prepared by the solid-state reaction method and were characterized by X-ray diffraction and magnetization measurements. A single spinel phase was obtained in the range 0.00?x?0.03$0.00?x?0.03$. The lattice parameter was found to increase at x=0.01$x=0.01$ and then decreases up to x=0.03$x=0.03$, which may indicate a distortion in the spinel lattice. The saturation magnetization was found to decrease with the increase in x up to 0.04, due to the replacement of the Fe³⁺ ions by the Sm³⁺ ions.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

Electrical conduction and magnetoelectric effect of (x) BaTiO3 + (1−x) Ni0.92Co0.03Cu0.05Fe2O4 composites in ferroelectric rich region

Particulate composites with composition (x)BaTiO₃+(1−x)Ni_0.92Co_0.03Cu_0.05Fe₂O₄ in which x varies as 1, 0.85, 0.70, 0.55 and 0 (in mol%) were prepared by the conventional double sintering ceramic technique. The presence of two phases viz. ferromagnetic (Ni_0.92Co_0.03Cu_0.05Fe₂O₄) and ferroelectric (BaTiO₃) was confirmed by X-ray diffraction analysis. The dc resistivity and thermo-emf measurements were carried out with variation of temperature. The ac conductivity (σ_ac) measurements investigated in the frequency range 100 Hz to 1 MHz conclude that the conduction in these composites is due to small polarons. The variation of dielectric constant and loss tangent with frequency (20 Hz to 1 MHz) was studied. The static magnetoelectric conversion factor, i.e. dc (dE/dH)_H was measured as a function of intensity of applied magnetic field. The changes were observed in electrical properties as well as in magnetoelectric voltage coefficient as the molar ratio of the constituent phases was varied. A maximum value of magnetoelectric conversion factor of 536.06 μV/cm Oe was observed for the composite with 70% BaTiO₃+30% Ni_0.92Co_0.03Cu_0.05Fe₂O₄ at a dc magnetic field of 2.3 K Oe. The maximum magnetoelectric conversion output has been explained in terms of ferrite-ferroelectric content, applied static magnetic field and resistivity.