B nuclear magnetic resonance study of boron nitride nanotubes prepared by mechano-thermal method

We reported ¹¹B nuclear magnetic resonance studies of boron nitride (BN) nanotubes prepared by mechano-thermal route. The NMR lineshape obtained at 192.493 MHz (14.7 T) was fitted with two Gaussian functions, and the ¹¹B nuclear magnetization relaxations were satisfied with the stretched-exponential function, exp[-(t/T₁)^(D+1)/6] (D: space dimension) at all temperatures. In addition, the temperature dependence of spin-lattice relaxation rates was well described by (a: constant, T: temperature) and could be understood in terms of direct phonon process. All the ¹¹BNMR results were explained by considering the inhomogeneous distribution of the paramagnetic metal catalysts, such as α-Fe, Fe-N, and Fe₂ B, that were incorporated during the process of high-energy ball milling of boron powder and be synthesized during subsequent thermal annealing. X-ray powder diffraction as well as electron paramagnetic resonance (EPR) on BN nanotubes were also conducted and the results obtained supported these conclusions.     

Mott-type hopping conduction in the ordered and disordered phases of LiCoO2

The temperature dependence of dc resistance was observed in the range of for layered-rock-salt (hexagonal structure, ordered distribution between Li and Co) and modified-spinel (cubic, random distribution) phases of LiCoO₂. The results suggest Mott-type hopping conduction arising from the localized Co-3d electrons in the valence band. The densities of states (DOS) at the Fermi energy (E_F) estimated from the slope of the resistance curves were 2.0×10²⁰ and 5.5×10¹⁹ cm⁻³ eV⁻¹ for the ordered and disordered phases, respectively. The relatively low DOS at E_F in the disordered phase suggests that E_F approaches the edge of the valence band as a result of the narrowing of Co-t_2g bands due to the higher lattice symmetry in the disordered phase.     

Molecular dynamics of [(CH2OH)3CNH3]2SiF6 by phase transition of 178 K

We have investigated the molecular motions of TRIS⁺ ([(CH₂OH)₃CNH₃]⁺) and ions in the [(CH₂OH)₃CNH₃]₂SiF₆ crystal below room temperature from the measurements of the spin-lattice relaxation time T₁ and the NMR absorption line of ¹H and ¹⁹F nuclei, in order to elucidate the changes of the molecular motions by the phase transition of T_c=178 K. The narrowing of the ¹⁹F-NMR line was observed around T_c=178 K and the reorientation of the anion appears above T_c. Moreover, from the analysis of the temperature dependence of T₁, we have observed that the activation energy of the reorientational motion of ions changes from 0.168 eV (T>T_c) to 0.185 eV (T<T_c). Based on these results, we found that the reorientational motion of ions is closely related to the origin of the phase transition at T_c. In addition, from the measurement of the ¹H-NMR line, we also found that the reorientational motion of H₂ in the -CH₂OH group becomes active accompanied by the phase transition.     

Effect of Mn-doping on the electrical properties of Cu2GeSe3

In this work we report the temperature dependence of the resistivity ρ of p-Cu₂GeSe₃ and manganese-doped p-Cu₂GeSe₃ at low temperature. It was found that for a intrinsic sample ρ obeys the Shklovskii-Efros-type variable-range hopping resistivity law in the temperature range from 4 to 63 K. This behaviour is governed by generation of a Coulomb gap Δ=78 meV in the density of localized states. We find a low activation term T₀=0.24 K, which is an indication of a large localization length ξ. For Mn-doped sample a metal-insulator transition (MIT) is observed at T=65 K. On the basis of the Mott criterion for metal-insulator transition, the critical carrier density n_c is determined. From the analysis of resistivity data it is concluded that Mn acts as acceptor impurity.     

Transport properties and magnetoresistance in CoNb1−xMnxSb half-Heusler alloys with a low temperature localization

The transport properties and magnetoresistance of half-Heusler CoNb_1−xMn_xSb (x=0.0-1.0) alloys have been investigated between 2 and 300 K. In this temperature range, a metallic conductivity has been observed for the alloys with higher (x=1.0) and lower (x=0.0-0.2) Mn contents. However, the middle Mn content alloys (x=0.4-0.8) exhibit non-metallic conductive behavior. Their temperature dependence of resistivity undergoes a Mott localization law ρ=ρ₀exp(T₀/T)^p (p=1/4) rather than a thermal excitation regime ρ=ρ₀exp(E_a/kT) at low temperature (). The localization can be attributed to atomic and magnetic disorder. Resistivity peaks from 25 to 300 K were also observed for these alloys. Magnetotransport investigation reveals that these resistivity peaks result from localization effect as well as spin-disorder scattering.     

Metal-insulator transition and variable-range hopping conductivity of n-CdSb in magnetic field

Resistivity, ρ, of a II-V group semiconductor n-CdSb doped with In is investigated in pulsed magnetic fields up to and at temperatures . The low-temperature resistivity ρ(T) increasing with T in the range of B<4 T is found to have an upturn around B∼4 T and strong activated behavior at further increase of B. These observations give evidence for magnetic-field-induced metal-insulator transition (MIT). In the insulating side of the MIT, Mott variable-range hopping (VRH) conductivity with two types of asymptotic behavior, ln ρ (T, B)∼T^−3/4B² and ln ρ (T, B)∼(B/T)^1/3, is established in low and high magnetic fields, respectively. The VRH conductivity is analyzed using a model of the near-edge electron energy spectrum established by investigations of the Hall effect. The VRH conductivity is shown to take place over the band tail states of one out of two impurity bands, which for T=0 and B=0 lie above the conduction band edge.     

Crystal field effect and geometric frustration in Er2Ti2O7 —an XY antiferromagnetic pyrochlore

Magnetic susceptibility of powder Er₂Ti₂O₇ (ErT) is measured between 300 K and 80 K. shows a Curie-Weiss (CW) type behaviour with   ErTiO_3.5 and . A crystal field (CF) analysis of our experimental data, g-values (g_∥=0.27 and g_⊥=7.8) and the positions of two CF levels (reported earlier from an inelastic neutron scattering study) provide CF parameters and CF levels of the ground ⁴I_15/2 and excited multiplets of ErT. The theoretical follows a CW-type behaviour, with . Single-ion magnetic anisotropy (χ_⊥−χ_∥) is 9500×10⁻⁶ emu/mol ErTiO_3.5 at 300 K, which increases by ∼54 times at 10 K and ErT resembles an XY planar system. It can be inferred from CF analysis that the earlier observed change of from −13 K to −22 K below 50 K is not due to the CF effect. Nuclear hyperfine (HF) levels of ¹⁶⁷ErT and ¹⁶⁶ErT are calculated and the theoretical curve of vs. T (K) for T<T_N matches the observed results. Mössbauer lines expected for ¹⁶⁶ErT are also predicted.     

Effects of Zn substitution on the magnetic and transport properties of La0.6Sr0.4Mn1−yZnyO3−δ (0≤y≤0.3)

Phase-singular solid solutions of La_0.6Sr_0.4Mn_1−yZn_yO_3−δ(0≤y≤0.3) [LSMZO] perovskite of rhombohedral symmetry (space group: ) with y up to 30 at.% could be synthesized notwithstanding the differences in ionic radii of Mn_{V I}³⁺ (i.r.=0.645 Å) and Zn_{V I}²⁺ (i.r.=0.74 Å). The LSMZO≤02 compositions are ferromagnetic metallic (FMM) at room temperature whereas LSMZO-02-08 are ferromagnetic insulators (FMI) and LSMZO>08 are paramagnetic insulators (PMI). Total obliteration of the FM transition is unique to Zn-doping at leading to PMI even at low temperatures, measured up to 8 K (presently). The FM to PM transition (T_c) and the peak (T_p) in resistivity-temperature curves decreases with the Zn-content. The charge-transport in p-type LSMZO is predictable by variable range hopping (VRH), which changes to nearest-neighbor hopping of small polarons (NNHP) at T>T_p. Non-stoichiometry (0.005≤δ≤0.21) evaluated chemically from redox titrations indicated the prevalence of excess oxygen vacancy rather than charge compensatively predictable values which, in turn, indicates the diminishing Mn⁴⁺ content in LSMZO. The ’s act as electron donors in p-LSMZO and this increases the resistivity (ρ_RT) associated with the shift in T_c to low temperatures. Increased ρ_RT on annealing in low is a clear evidence on the role of in LSMZO.     

Quadratic temperature dependence of electron-phonon scattering in disordered V1−xPdx alloys

We report the results of a comprehensive study of weak localization and electron-electron interaction effects in disordered V_1−xPd_x alloys whose compositions are close to the (low T_c) A15 V₃Pd compound. Magnetoresistivity and zero field resistivity have been measured within the temperature range 1.5≤T≤300 K. The low-temperature resistivity obeys a law, which is explained by electron-electron interaction. We have determined the electron-phonon scattering time (τ_e-ph) for V_1−xPd_x alloys. Our results indicate an anomalous electron-phonon scattering rate obeying quadratic temperature dependence. This observation is interpreted by the existing theories of electron-phonon interactions.     

Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeFe(dto)3] (dto=C2O2S2)

(n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] shows a new type of first order phase transition called charge-transfer phase transition around 120 K, where the charge transfer between Fe^II and Fe^III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal structure at room temperature. Crystal data: space group P6₃, Z=2. Moreover, we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased, the a-axis, which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe^IIFe^III(dto)₃]_∞, contracts by 0.1 Å at the charge-transfer transition temperature (T_CT), while the c-axis, perpendicular to the honeycomb network layer, elongates by 0.1 Å at T_CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T_CT, which is responsible for the quite small vibrational contribution to the entropy change, compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] is regarded as spin entropy driven phase transition.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

Spin-glass behavior and magnetocaloric effect in melt-spun TbCuAl alloys

Magnetic properties and magnetocaloric effects of amorphous and crystalline TbCuAl ribbons are investigated by measuring their ac susceptibilities including a nonlinear term and dc magnetizations. The in-phase third harmonic ac susceptibility is found to be negative. It can be well fitted by the expression at high temperatures, indicating a spin-glass behavior in amorphous TbCuAl alloy. ΔT_f(ω)/[T_f(ω)Δlog₁₀ω], a possible distinguishing criterion to judge the presence of a spin-glass behavior is ∼0.011. The frequency-dependent data can be well fitted by the conventional critical slowing down law and the spin-glass transition temperature is obtained to be 20.1 K. The maximum of magnetic entropy change reaches 4.5 J kg⁻¹ K⁻¹ for a field change of 0-50 000 Oe, while the crystalline TbCuAl compound experiences a simple ferromagnetic-to-paramagnetic phase transition. The peak value of magnetic entropy change is obtained at the Curie temperature and reaches 14.4 J kg⁻¹ K⁻¹ for the same field change, which is much larger than that of amorphous TbCuAl alloy.     

Effect of pseudogap on the positronium in void

In ceramic high-Tc superconductor (Bi, Pb)₂Sr₂Ca₂Cu₃O₇ the anomalies in temperature dependence τ₂(T)-lifetime of positrons trapped by microvoids are observed in Tc-region [V.L. Sedov, S.N. Kuznetsov, O.A. Tsigelnik, N.N. Oleynikov, D.I. Grigorashev, Phys. Lett. A 222 (1996) 455; D. Sanyal, D. Banerjee, U. De, Phys. Rev. B 58 (1998) 15226]. This effect is considered on the basis of the model in which the positrons trapped in microvoids form positronium atoms, interacting with surrounding medium by the processes Ps↔e⁺+e⁻ [V.L. Sedov, O.A. Tsigelnik, Phys. Lett. A 332 (2004) 423]. It is shown that the local density of states of the interacting positronium forms the δ-peak near the lower boundary of the gap 2Δ at ω>−Δ. The conclusion was made that the experimentally observed discontinuous increase τ₂ at the transition of the superconducting phase into pseudogap state is the result of the discontinuous increased weight of the peak at this transition.     

Structural characterization and electrical properties of quaternary CdGaInSe4 thin films

Stoichiometric bulk ingot material of the quaternary CdGaInSe₄ was prepared by direct fusion of the constituent elements in vacuum-sealed silica tubes. Nearly stoichiometric films could be deposited by thermal evaporation of the ingot material in 10⁻³ Pa vacuum at a deposition rate 1.5 nm/s. Crystal structure investigation was carried out using X-ray diffractometry and transmission electron diffraction. Elemental composition was determined by means of energy-dispersive X-ray spectrometry. CdGaInSe₄ possesses a tetragonal defective chalcopyrite structure (space group ) with lattice parameters a=0.5665 nm and c=1.1221 nm. All the films exhibited n-type conduction and ohmic behaviour with metallic films of Au, Cd, In, Ag and Sb. However, in the case of Al a nonlinear behaviour occurs. Analysis of the temperature dependence of the dark conductivity in the range 130-470 K has revealed three operating conduction mechanisms; a variable range hopping conduction process dominating at low temperatures below 270 K, followed by a transport of the charge carriers across intercrystalline barriers and grain boundaries in the temperature range 270-353 K, and finally an extrinsic conduction above 353 K.     

A study on new phase transitions in Cs2CaCl4·2H2O single crystals by observation of Cs NMR

The ¹³³Cs 1/2→−1/2 spin-lattice relaxation rate, , and the spin-spin relaxation rate, , for a Cs₂CaCl₄·2H₂O single crystal have been measured in function of temperature. The dominant relaxation mechanism of this crystal over the whole temperature range investigated here proceeds via quadrupole interaction. The changes in the ¹³³Cs spin-lattice relaxation rate near 325 K (=T_c1) and 360 K (=T_c2) correspond to phase transitions in the crystal. The change in the spin-lattice relaxation rate at T_c1 is small because the crystal lattice does not change very much during this phase transition. The change in near T_c2 is due to the critical slowing down of the soft mode that typically occurs in structural phase transitions. The temperature dependence of the spin-lattice relaxation rate for this crystal has maximum values at about 240 K, which is attributable to the effect of molecular motion as described by Bloembergen-Purcell-Pound theory. The phase transition temperatures T_c1 and T_c2 obtained from the temperature dependence of the relaxation rate is also clear from data obtained using differential scanning calorimetry. Therefore, we know that previously unreported phase transitions occur at 325 and 360 K.     

Magnetic study of Mg0.95Mn0.05Fe2O4 ferrite nanoparticles

The magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite samples with an average particle size of ∼6.0±0.6 nm have been studied using X-ray diffraction, Mössbauer spectroscopy, dc magnetization and frequency dependent real χ^′(T) and imaginary χ^″(T) parts of ac susceptibility measurements. A magnetic transition to an ordered state is observed at about 195 K from Mössbauer measurements. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization have been recorded at low field and show the typical behavior of a small particle system. The ZFC curve displays a broad maximum at , a temperature which depends upon the distribution of particle volumes in the sample. The FC curve was nearly flat below , as compared with monotonically increasing characteristics of non-interacting superparamagnetic systems indicating the existence of strong interactions among the nanoparticles. A frequency-dependent peak observed in χ^′(T) is well described by Vogel-Fulcher law, yielding a relaxation time and an interaction parameter . Such values show the strong interactions and rule out the possibility of spin-glass (SG) features among the nanoparticle system. On the other hand fitting with the Néel-Brown model and the power law yields an unphysical large value of τ₀ (∼6×10⁻⁶⁹ and 1.2×10⁻²² s respectively).