Magnetic phase transitions and magnetoresistance in the La0.7Ba0.3(Mn1−xMex)O3 (Me=Fe,Al) single crystals and La0.7Sr0.3(Mn1−xMex)O3 (Me=Fe,Cr, Al) ceramics

The single crystals of La_0.7Ba_0.3(Mn_1−xFe_x)O₃ (x⩽0.28) and La_0.7Ba_0.3(Mn_1−xAl_x)O₃ (x⩽0.15) compositions were grown using flux method and characterized by X-ray, electrical and magnetization measurements. The Fe-doping above x=0.2 destroys a long range ferromagnetic order thus leading to a spin glass state. It is found that insulating spin glasses exhibit a large magnetoresistance in the paramagnetic region which is comparable to that for ferromagnetic crystals showing metal–insulator transition close to T_C. The magnetic behavior of La_0.7Ba_0.3(Mn_1−xMe_x)O₃ (Me=Fe, Cr, Al) ceramics is in agreement with superexchange magnetic interactions via oxygen.     

X-ray diffraction and Mössbauer Studies of γ′-(Fe1−xSnx)4N compounds (0.0⩽x⩽0.3)

The structure and magnetic properties of γ′-(Fe_1−xSn_x)₄N samples have been studied using X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy. It has been shown that the single-phase (Fe_1−xSn_x)₄N compounds can be prepared in the composition range of 0.0⩽x⩽0.3, which have the similar structure as γ′-Fe₄N The lattice parameter with the increase of Sn concentration can be well fitted with two linear relationships a₀(x)=3.795+0.019x (with x⩽0.10 ) and a₀(x)=3.797+0.228(x−0.10) (with 0.1⩽x⩽ 0.3). The fitting results of Mössbauer spectra indicate that the hyperfine parameters have the same changing tendency with lattice parameter, and the Sn atoms have a preference to be located at the corner site.     

IR optical absorption and reflection spectra in narrow gap semiconductors

Light transmission T(λ) and reflection R(λ) spectra were measured for the crystals Cd_xHg_1−xTe (x = 0.26). InSb and Mn_xHg_1−xTe (x = 0.12) with low impurity content at T = 300 K in the wavelength range 2.5 μm ⩽ λ ⩽40 μm. From the measured T(λ) and R(λ) data a dependence of the absorption coefficient x(λ) for the free-carriers light absorption (FCLA) was derived, which is caused by the intrabund electron and hole transitions and the intcrband transitions of the heavy holes from the band V₁ to the band V₂ of the light holes: x(λ) = x_intraband(λ) + x_interband(λ).It is concluded from the quantum mechanical approach that the intraband FCLA is directly related with the carriers scattering mechanisms. Calculations of x_intraband(λ) within the framework of this approach demonstrated that under room temperature the major contribution was from the scattering by polar optical phonons. In the case of less perfect Mn_xHg_1−xTe however, one should take into account the scattering by the short-range potentials of the defects.     

Theoretical investigation of electronic structure and optical response in relation to the transport properties of Ga1−xInxN (x = 0, 0.25, 0.50, 0.75)

The state-of-the-art all-electron FLPAW method and the BoltzTrap software package based on semi-classical theory were adopted to explore the electronic structure and the optical and thermoelectric properties of Ga_1−xIn_xN. Ga_1−xIn_xN is predicted to be a direct band gap material for all values of x. Moreover, the band gap varies between 2.99 eV and 1.95 eV as x changes. Optical parameters such as the dielectric constant, absorption coefficient, reflectivity and refractive index are calculated and discussed in detail. The doping of In plays an important role in the modulation of the optical constants. The static dielectric constant ɛ(0) of Ga_1−xIn_xN was calculated as 3.95, 3.99, 3.99 and 4.03 at x = 0.00, 0.25, 0.50 and 0.75, respectively. The static refractive index is 2.0 for pure Ga_1−xIn_xN at x = 0.00. The thermal properties varied greatly as x fluctuated. The ternary alloy has large values for the Seebeck coefficient and figure of merit at high temperatures and is thus suitable for thermoelectric applications. Pure Ga_1−xIn_xN at x = 0 exhibited ZT = 0.80 at room temperature, and at higher temperatures, the thermal conductivity decreased with increased In doping.     

Substitutional effects on the electrical properties of the purple bronze Li0.9Mo6O17

Dopant-level substitution of tungsten for molybdenum in Li_0.9Mo_6−xW_xO₁₇ solid solutions is shown to have a large effect on the electrical transport properties, which might be attributed to W interfering with the overlap of t_2g 4d Mo and π 2p orbitals forming the conduction band. With increasing concentration of W, the metal-to-metal transition broadens and shifts to higher temperature. At ∼6 at.% W content the material becomes semiconducting. Effects on the electronic properties are much less dramatic by alkali metal substitution in (Na_1−xLi_x)_0.9Mo₆O₁₇ alloys, since the alkali metals are only indirectly involved in the formation of the band structure. With x = 0, 0.25 and 0.5 the electrical resistivity behaves similar to Na_0.9Mo₆O₁₇. At x = 0.75 the electrical transport properties are nearly identical to that Li_0.9Mo₆O₁₇ and the supercond uctivity at 2 K is still observed.     

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

The monoclinic phase (P2₁/n) was formed for 0≤x≤0.6 and the NASICON-type rhombohedral phase (R3̄c) was obtained for the region 0.8≤x≤1.2 in the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The activation energy for Li⁺ migration was ca. 0.45 eV for the monoclinic structure and ca. 0.36 eV for the rhombohedral structure. The maximum conductivity of 8.4×10⁻⁶ S cm⁻¹ at 298 K was obtained for x=0.8 of the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The conductivity of LiCrTa(PO₄)₃ was enhanced about three to five times by the addition of the lithium salt due to the improvement of the sinterablity. The maximum conductivity was 2.4×10⁻⁵ S cm⁻¹ at 298 K for LiCrTa(PO₄)₃–0.2Li₃BO₃.     

Insulator-superconductor-metal transitions induced by spin fluctuations in the paramagnetic phase of doped insulators

AbstractThe band structure of cuprates as a doped 2D insulator is modeled assuming that the excess charge carriers are associated with the corresponding substitution atoms, and the phase diagram of the paramagnetic states as a function of the degree x of doping at zero temperature is studied. The Hamiltonian contains electronic correlations on impurity orbitals and hybridization between them and the initial band states of the insulator. It is shown that the change in the electronic structure of a doped compound includes the formation of impurity bands of distributed and localized electronic states in the initial insulator gap. It is established that in the case of one excess electron per substitution atom the spin fluctuations (1) give rise to an insulator state of the doped compound for x < x _thr, 1, (2) lead to a superconducting state for x _thr, 1 < x < x _thr, 2, and (3) decay as x > x _thr, 2 increases further, and the doped compound transforms into a paramagnetic state of a “poor” metal with a high density of localized electronic states at the Fermi level.     

Observations of multi-phase microstructures in R2(Fe1−xCox)14B where R=Nd or Dy

Multi-phase microstructures were observed in the psuedo-quaternary phase field of the 2–14–1 magnet materials Nd₂Fe₁₄B, Nd₂Co₁₄B, Dy₂Fe₁₄B, and Dy₂Co₁₄B. At equilibrium, (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B had heretofore been widely assumed to be single phase where 1>x>0 and 1>y>0. In this study, three-phase microstructures were observed in (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B when x>0.3 and y>0.5. The Curie temperatures and peritectic decomposition temperatures for Nd₂(Fe_1−xCo_x)₁₄B are reported for several values of x in the range 1>x>0.     

Pseudogap and metal-insulator transitions in doped semiconductors

The electronic spectrum of a doped semiconductor described by the Anderson-Holstein impurity model and its conductivity derived from the Kubo linear response theory are calculated. Two characteristic temperatures depending on the doping level x are found in the phase diagram, T _PG and T _λ(x). The pseudogap that opens in the single-particle spectrum at low doping levels and temperatures closes at the lower one, T _PG. The pseudogap state of an insulator is attributed to spin fluctuations in a doped compound. At the higher characteristic temperature T _λ(x),, spin fluctuations vanish and the doped compound becomes a paramagnetic poor metal. Two distinct metal-insulator crossovers between semiconductor-like and metallic temperature dependence of resistivity are found. An insulator-to-poor-metal transition occurs at T ^*(x) ≈ T _λ(x). A poor-metal-to-insulator transition at a lower temperature is attributed to the temperature dependence of density of states in the pseudogap. It is shown that both transitions are observed in La_2?x Sr_xCUO₄.     

Superconductivity in LaSr(Ba)CuO and related systems

Systematics in the superconducting behaviour of Ln _2−xSr _x(Ba _x)CuO ₄, La _2−xSr _x−yBa _y(Ca _y)CuO ₄, (La _1−xLn _x) _2−ySr _y(Ba _y)CuO ₄ with Ln = Pr, Nd or Y and related systems are presented. The role of oxygen stoichiometry and lattice parameters of these mixed valent copper oxides is indicated. These high T _c superconducting oxides exhibit high-temperature resistivities in the borderline of the metal-nonmetal transition.     

High temperature superconductivity in (M1−xM′x)2CuO4−δ and related compounds (M = Y,La, Eu,Sm; M′ = Ba,Sr)

Compounds of the form (M_1−xM′_x)₂CuO_4−δ and related compounds where M and M′ are Y, various rare earths from La to Lu, and the alkaline earths Sr and Ba, have been investigated in connection with high temperature superconductivity. High temperature superconductivity is confirmed for the system (La_1−xBa_x)₂CuO_4−δ, (La_1−xSr_x)₂CuO_4−δ and (Y_1−xBa_x)₂CuO_4−δ with superconducting transition temperature T_c onsets of 30 K, 38 K and 90 K, respectively. We have found that the related systems (Eu_1−xBa_x)₂CuO_4−δ and (Sm_1−xBa_x)₂CuO_4−δ also exhibit high temperature superconductivity with T_c onsets of 95 K and 65 K, respectively. The highest T_c onset observed in this investigation was 97 K for a sample with the nominal composition of the spinel structure Y_0.33Ba_0.67Cu₂O_4−δ. Measurements of the specific heat C as a function of temperature T on a La_0.8Sr_0.2CuO_4−δ sample reveal a break in slope in the C/T vs T curve at the T_c midpoint, but no clearly discernable jump in C at T_c. A linear term ≈ λ′T in C was observed at low temperature in the superconducting state.     

Synthesis and characterisation of Cr3+-containing NASICON-related phases

Chromium-containing NASICON-related phosphates of the type Na_(1+x)Cr_xM_(2−x)P₃O₁₂) (M = Ti, Hf, Zr) have been synthesised by solid state reaction and structurally characterised by Rietveld refinement of the powder X-ray diffraction data. Materials of composition A_(1+x)/2Cr_xZr_(2−x)P₃O₁₂ (A = Cd, Ca, Sr), have also been prepared and characterised. The crystal structure of Na_(1+x)Cr_xM_(2−x)P₃O₁₂ corresponds to R-3c symmetry for x values ranging from 0.15 to 2.00, whereas compounds of composition A_(1+x)/2Cr_xZr_(2−x)P₃O₁₂ corresponding to R-3c are obtained when x ≤ 1.00 for Sr²⁺ and Ca²⁺, and x ≤ 1.50 for Cd²⁺. The polarizing effect of the two different metal ions A and M on the phosphorus atom and the P–O bond was studied by both ³¹P MAS NMR and infrared spectroscopy and shows that the electron density on the phosphorus, and thus the strength of the P–O bonds, are affected by both the interstitial (A) and the structural (M) metal ions.     

Modeling of band discontinuity using modified Harrison model

Modeling of the valence band discontinuity was proposed with Harrison model modified by introducing the effective bond length for AlX (X = P, As, Sb). The valence band discontinuity of heterostructures including AlX as constituent, for example, GaAs/Al_xGa_1−xAs and Al_xIn1_1−xAs/ In_xGa_1−xAs, was predicted. The predicted values were in good agreement with the experimental values, different from ordinary Harrison model. Prediction of the valence band discontinuity of quarternary alloy (Al_xGa_1−x)_y In_1−yP lattice matched to GaAs was also attempted.     

Electrical properties of V2O5B2O3 glasses

Binary semiconducting glasses of xV₂O₅·(1−x)B₂O₃ system with x ranging from 0.6 to 0.9 have been investigated to elucidate their electronic conduction. The values of conductivity and activation energy of these glasses are in good agreement with previous results on most V₂O₅-based glasses. Arguments for the small-polaron as the charge carrier in V₂O₅B₂O₃ glasses are presented.     

Magnetite-cobalt ferrite nanoparticles for kerosene-based magnetic fluids

Due to the magnetic anisotropy introduced by the Co²⁺ ion in octahedral sites of cubic spinel ferrites, it is possible to tailor the magnetic properties by changing the cobalt content. Magnetic fluids with magnetite-cobalt ferrite nanoparticles given by the formula Co_(x)Fe_(3−x)O₄ with x=0, 0.2 and 0.4 were prepared. Kerosene and oleic acid were used as liquid carrier and surfactant, respectively. Spherical magnetic nanoparticles were obtained by coprecipitation from metal salts and ammonium hydroxide; afterwards the magnetic fluids were obtained by a peptization process. Powder properties were characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption isotherma (BET), vibrating sample magnetometry (VSM) and fluids by transmission electron microscopy (TEM), thermogravimetric analyzer (TGA), VSM and the short-circuited transmission line technique.     

Spectromicroscopic investigation of (NH4)2S treated polycrystalline Cu(In1−xGax)Se2

Device-grade polycrystalline thin-film Cu(In_1−xGa_x)Se₂ was treated with (NH₄)₂S at 60°C to determine the resulting microscopic surface composition/morphology. Scanning electron microscopy was used to evaluate the resultant macroscopic surface morphology. Modification of the surface and grain boundary chemistry of the Cu(In_1−xGa_x)Se₂ polycrystalline films was investigated with scanning photoemission spectromicroscopy. The submicrometer lateral resolution of this technique allows us to directly characterize not only the surface chemistry of the treated films on the submicron scale, but also to probe the grain boundary chemistry. Chemical maps depicting the distribution of chemical species on the surface and at grain boundaries were obtained by monitoring the S 2p, Se 3d, In 4d/Ga 3d and Cu 3d (valence band) photoelectrons while scanning the sample. Background maps were also acquired of each of the peak energies to separate chemical contrast from topographic contrast. Results show that S has been incorporated at the surface, possibly creating a wider bandgap Cu(In_1−xGa_x)(Se_1−yS_y)₂ surface layer, and along the grain boundaries. The purpose of this investigation is to find an environmentally safe replacement for the toxic CdS overlayer commonly used for heterojunction devices without sacrificing overall device performance and reliability.     

Dielectric,electrical transport and magnetic properties of Er3+substituted nanocrystalline cobalt ferrite

Erbium substituted cobalt ferrite (CoFe_2−xEr_xO₄; x=0.0–0.2, referred to CFEO) materials were synthesized by sol-gel auto-combustion method. The effect of erbium (Er³⁺) substitution on the crystal structure, dielectric, electrical transport and magnetic properties of cobalt ferrite is evaluated. CoFe_2−xEr_xO₄ ceramics exhibit the spinel cubic structure without any impurity phase for x≤0.10 whereas formation of the ErFeO₃ orthoferrite secondary phase was observed for x≥0.15. All the CFEO samples demonstrate the typical hysteresis (M–H) behavior with a decrease in magnetization as a function of Er content due to weak superexchange interaction. The frequency (f) dependent dielectric constant (ε′) revealed the usual dielectric dispersion. The ε′–f dispersion (f=20 Hz to 1 MHz) fits to the modified Debye's function with more than one ion contributing to the relaxation. The relaxation time and spread factor derived are ∼10⁻⁴ s and ∼0.61(±0.04), respectively. Electrical and dielectric studies indicate that ε′ increases and the dc electrical resistivity decreases as a function of Er content (x≤0.15). Complex impedance analyses confirm only the grain interior contribution to the conduction process. Temperature dependent electrical transport and room temperature ac conductivity (σ_ac) analyses indicate the semiconducting nature and small polaron hopping.     

Thermal dependence of conduction properties in the Bi2O3Pb2OF2 system

Conduction properties of bismuth-lead oxyfluorides (Bi,Pb)₂(O,F)₃ have been investigated by complex impedance analysis. A special attention has been drawn to a hexagonal solid solution Bi_(1−x)Pb_xO_(1.5−x)F_x (0.45⩽x⩽0.741 at 770 K), which is isostructural with ALa₂O₃. Conductivity values range from 3 × 10⁻⁵ to 3 × 10⁻² (ω cm)⁻¹ at 585 K. A minimum associated with a maximum in activation energy is observed for the composition x = 0.5 i.e. BiPbO₂F.     

Structural chemistry and zeolitic properties of mixed oxalates with two open-framework types based on eight coordinate metals

Two families of open-framework materials have been obtained from the assembly of MO₈ polyhedra and oxalate groups as building blocks. The compounds can be formulated as [MM′(C₂O₄)₄]²⁻(M″_y)²⁺ · (4 + x)H₂O (y is 2 for monovalent M″ metals and 1 for divalent M″ metals), in which the sum of the valences of the two metals M and M′ involved in the anionic framework is six. The water molecules and counter cations, located in the voids of the structure, lead to zeolitic or cation dynamic properties.     

Effects of Co substitution on structural and magnetic properties of R3(Fe1−xCox)29−yVy (R=Tb,Dy)

Synthesis of two novel series of intermetallic compounds Tb₃(Fe_1−xCo_x)_27.4V_1.6 (x=0,0.1, 0.2, 0.3, 0.4) and Dy₃(Fe_1−xCo_x)_27.8V_1.2 (x=0, 0.1, 0.2, 0.3) with the monoclinic Nd₃(Fe,Ti)₂₉-type structure (3:29) is presented. In the Dy series for x=0.4 a disordered variant of the hexagonal Th₂Ni₁₇-type structure is formed. The cell parameters decrease and the Curie temperature increases with increasing of the Co content. In the case of the Tb₃(Fe_1−xCo_x)_27.4V_1.6 series in the M(T) curve a magnetic transition is observed which is attributed to spin reorientation phenomena. This critical temperature decreases with increasing Co from 473 K for x=0.1 to 393 K for x=0.3, and was not observed in the case of 0.4. XRD patterns of magnetically aligned powder samples reveal the presence of a tilted magnetic structure.