Strong magnetoelastic effect in Pr1−xCaxMnO3

Manganese oxides with distorted perovskite structure have attracted much attention during the last decade due to their colossal magnetoresistance (CMR), and the strong correlations among the various degrees of freedom involved. In particular, Pr_1−xCa_xMnO₃ compounds present in a wide Ca-doping range a charge ordering phenomenon, consisting of real space ordering of Mn³⁺ and Mn⁴⁺ in alternate lattice sites below a certain temperature T_CO. This ordering brings about a lattice distortion and a large hardening of the sound velocity below T_CO. Tomioka et al. have observed that an applied magnetic field can melt this charge ordered state and induce a transition from an insulating to a metallic state. In order to study the effects of this charge order melting, ultrasonic longitudinal sound velocity measurements were performed on polycrystalline Pr_1−xCa_xMnO₃ (x=0.35 and 0.5) as a function of magnetic field and temperature. Interesting anomalies were found related to the melting of the charge ordered phase into a metal-like state even at low temperatures.     

Bond-lengths of the atomic nearest-neighbor and next-nearest-neighbor in A1−xBxC1−yDy III–V solid solutions

On the basis of the FDUC model and the hypothesis of the constant covalent radii, the expressions of the atomic nearest-neighbor and the next-nearest-neighbor bond-lengths were derived for A_1−xB_xC_1−yD_y III–V quaternary solid solutions. This set of bond-length expressions predicts the averaged bond-lengths and bond angles at any concentration (x, y) for the III–V pseudobinary and quaternary solid solutions, which are only dependent on the lattice parameters and the concentrations of the pure end compounds. When x=0, 1 or y=0, 1, A_1−xB_xC_1−yD_y III–V quaternary solid solutions degenerate into the relative pseudobinary solid solutions, in which the nearest-neighbor and the next-nearest-neighbor bond-lengths agree well with the experimental results. Further discussion and comparison with other theoretical models are also given in this paper.     

Characterization of GaN epitaxial layers on SiC substrates with AlxGa1−xN buffer layers

High quality GaN epitaxial layers were obtained with Al_xGa_1−xN buffer layers on 6H–SiC substrates. The low-pressure metalorganic chemical vapor deposition (LP-MOCVD) method was used. The 500 Å thick buffer layers of Al_xGa_1−xN (0≤x≤1) were deposited on SiC substrates at 1025°C. The FWHM of GaN (0004) X-ray curves are 2–3 arcmin, which vary with the Al content in Al_xGa_1−xN buffer layers. An optimum Al content is found to be 0.18. The best GaN epitaxial film has the mobility and carrier concentration about 564 cm² V⁻¹ s⁻¹ and 1.6×10¹⁷ cm⁻³ at 300 K. The splitting diffraction angle between GaN and Al_xGa_1−xN were also analyzed from X-ray diffraction curves.     

Structural relaxation and crystallisation of bulk metallic glasses Zr41Ti14Cu12.5Ni10−xBe22.5Fex (x = 0 or 2) studied by mechanical spectroscopy

The measurements of the internal friction and dynamic shear modulus as well as differential scanning calorimetry have been performed in order to investigate the structural relaxation and crystallization of Zr₄₁Ti₁₄Cu_12.5Ni_10−xBe_22.5Fe_x (x=0 or 2) bulk metallic glasses. It is found that the glass transition is retarded and the thermal stability of supercooled liquid is increased by the Fe addition. The experimental results are well analyzed using a physical model, which can characterize atomic mobility and mechanical response of disordered condensed materials.     

Relaxation peaks associated with the oxygen-ion diffusion in La2−xBixMo2O9 oxide-ion conductors

The effects of bismuth doping on the oxygen-ion diffusion in oxide-ion conductors La_2−xBi_xMo₂O₉ (x=0.05, 0.1, and 0.15) have been studied by both internal friction and dielectric relaxation techniques. Two internal friction peaks of relaxation type (P₁ and P₂ peak) were observed at a measurement frequency of 4 Hz around 380 and 430 K, respectively. As for the dielectric measurement, a prominent dielectric relaxation peak (P_d) was found in all the Bi-doped samples around 700 K at a measurement frequency of 50 kHz, which actually consists of two sub-peaks (denoted as P_d1 and P_d2 peak). With increasing Bi-doping content, two peaks shift to higher temperature and decrease in height, while the activation energy of both peaks increases. The main reason was interpreted as the introduction of the lone-pair electrons of bismuth, which tends to block the diffusion of oxygen ion.     

Photoluminescence study of the nitrogen content effect on GaAs/GaAs1 − xNx/GaAs/AlGaAs: (Si) quantum well

We study the effect of nitrogen content in modulation-doped GaAs/GaAs_1 − xN_x/GaAs/GaAlAs:(Si) quantum well using low-temperature photoluminescence spectroscopy. The samples were grown on GaAs (001) substrates by molecular-beam epitaxy with different nitrogen compositions. The variation of the nitrogen composition from 0.04% to 0.32% associated to the bi-dimensional electron gas gives a new interaction mode between the nitrogen localized states and the GaAs_1 − xN_x/GaAs energies levels. The red-shift observed in photoluminescence spectra as function of nitrogen content has been interpreted in the frame of the band anticrossing model.     

Crystal structure, thermal expansion and electrical conductivity of Nd0.7Sr0.3Fe1−xCoxO3 (0≤x≤0.8)

The crystal structure, thermal expansion and electrical conductivity of the solid solution Nd_0.7Sr_0.3Fe_1−xCo_xO₃ for 0≤x≤0.8 were investigated. All compositions had the GdFeO₃-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction (XRPD). The pseudo-cubic lattice constant decreased continuously with x. The average linear thermal expansion coefficient (TEC) in the temperature range from 573 to 973 K was found to increase with x. The thermal expansion curves for all values of x displayed rapid increase in slope at high temperatures. The electrical conductivity increased with x for the entire temperature range of measurement. The calculated activation energy values indicate that electrical conduction takes place primarily by the small polaron hopping mechanism. The charge compensation for the divalent ion on the A-site is provided by the formation of Fe⁴⁺ ions on the B-site (in preference to Co⁴⁺ ions) and vacancies on the oxygen sublattice for low values of x. The large increase in the conductivity with x in the range from 0.6 to 0.8 is attributed to the substitution of Fe⁴⁺ ions by Co⁴⁺ ions. The Fe site has a lower small polaron site energy than Co and hence behaves like a carrier trap, thereby drastically reducing the conductivity. The non-linear behaviour in the dependence of log σT with reciprocal temperature can be attributed to the generation of additional charge carriers with increasing temperature by the charge disproportionation of Co³⁺ ions.     

Combinatorial synthesis and rapid characterization of Mo1−xSnx (0x1) thin films

Thin films of Mo_1−xSn_x, continuously and linearly mapped for 0<x<1, have been prepared by d.c. magnetron sputter deposition under various growth conditions. X-ray diffraction results indicate that as x in high-pressure deposited Mo_1−xSn_x increases from 0 to approximately 0.45, the bcc lattice expands and no new phases are formed. At low deposition pressures, Mo₃Sn, a β-tungsten structured phase, is formed along with the bcc Mo–Sn solid solution for 0.1<x<0.3. The variation of the lattice parameter for this intermetallic phase also indicates that solid solutions, possibly of the form Mo_3+ySn, are being formed. These materials are of special interest as anode candidates in lithium-ion batteries.     

Salt-assistant combustion synthesis of nanocrystalline Nd2(Zr1 − xSnx)2O7 (0 ≤ x ≤ 1) solid solutions

Nanocrystalline Nd₂(Zr_{1 − x}Sn_x)₂O₇ series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.     

Synthesis, characteristics and oxygen-sensitive properties of SrMgxTi 1 − xO3 nanocrystals

SrMg_xTi_{1 - x}O₃ nanocrystals (x = 0.1–0.6) were synthesized by the stearic acid gel method. Powder samples were characterized by X-ray diffraction and X-ray photoelectron (XP) spectroscopy. The results showed that the lattice parameter a and the O 1s XP spectrum changed not only with the Mg content x but also with the grain size d of the samples. The conductivity of a thick film specimen fabricated on an aluminium oxide wafer was investigated in a nitrogen—oxygen atmosphere.     

Phase relations, lattice thermal expansion in Ce1−xEuxO2−x/2 and Ce1−xSmxO2−x/2 systems and stabilization of cubic RE2O3 (RE: Eu, Sm)

The phase relations in CeO₂–Eu₂O₃ and CeO₂–Sm₂O₃ systems have been established under slow-cooled conditions from 1400 °C. The two-phase relations differ as the CeO₂–Eu₂O₃ system showed only two monophasic phase fields, namely F-type cubic and C-type cubic, whereas CeO₂–Sm₂O₃ system showed three phase fields namely F-type cubic, C-type cubic and a biphasic field comprising of C-type cubic and monoclinic phase. An interesting observation of this investigation is the stabilization of C-type rare-earth oxide after Ce⁴⁺ substitution, which is attributed to decrease in average cationic size on Ce⁴⁺ substitution at RE³⁺ site. The lattice thermal expansion behavior of F-type solid solution and C-type solid solution in CeO₂–Eu₂O₃ system was investigated by high-temperature XRD.     

Mechanical characterization of Ni1−xZnxFe2O4 prepared by non-conventional methods

The mechanical properties like hardness, H_v and compressive strength, σ of Ni_1−xZn_xFe₂O₄ (x = 0.2, 0.3, 0.4 and 0.5) prepared by the non-conventional flash combustion and citrate-gel decomposition techniques are studied and reported. It is observed that there is an increase in hardness with zinc content as well as sintering temperature. The hardness in the order of 2.0–3.63 GPa and compressive strength in the order of 150–240 MPa are obtained for Ni–Zn ferrites prepared by these non-conventional techniques. The influence of density, porosity and microstructure on hardness and compressive strength of Ni–Zn ferrites with respect to sintering temperature was studied.     

Optical transitions near the band edge in bulk CuInxGa1−xSe2 from ellipsometric measurements

From the analysis of the variation of optical absorption coefficient with incident photon energy between 0.8 and 2.6 eV, obtained from ellipsometric data, the energy E_G of the fundamental absorption edge and E_G′ of the forbidden direct transition for CuIn_xGa_1−xSe₂ alloys are estimated. The change in E_G and the spin-orbit splitting Δ_SO=E_G′−E_G with the composition x can be represented by parabolic expression of the form E_G(x)=E_G(0)+ax+bx² and Δ_SO(x)=Δ_SO(0)+a′x+b′x², respectively. b and b′ are called “bowing parameters”. Theoretical fit gives a=0.875 eV, b=0.198 eV, a′=0.341 eV and b′=−0.431 eV. The positive sign of b and negative sign of b′ are in agreement with the theoretical prediction of Wei and Zunger [Phys. Rev. B 39 (1989) 6279].     

Photoelectrochemical properties of sol–gel-derived Ti1−xVxO2 solid solution film photoelectrodes

Ti_1−xV_xO₂ solid solution film photoelectrodes were prepared by the dip-coating sol–gel method. X-ray diffraction and X-ray photoelectron spectroscopy were employed to ensure the formation of the solid solution and their composition. Obvious photoresponses were observed in the visible region for the solid solution film electrodes with x0.05 and the red shift of the photoresponse was enhanced with increasing x. Moreover, the solid solution film electrodes were found to be photoelectrochemically stable. However, the onset potential of photocurrent shifted positively with increasing x. Band model of the solid solution was suggested to explain the effects of the vanadium incorporation on the photoelectrochemical properties.     

Characterization of CuIn1 − xAlxS2 thin films prepared by thermal evaporation

Ingots containing single crystals of the quaternary alloys CuIn_1 − xAl_xS₂ (CIAS) were grown by a horizontal Bridgman method for compositions with x = 0, 0.2 and x = 0.4. (CIAS) thin films were prepared by thermal evaporation technique on to glass substrates. Structural and optical properties of the films were studied in function of the Al content. Band gap, and absorption coefficients were determined from the analysis of the optical spectra (transmittance and reflectance as a function of wavelength) recorded by a spectrophotometer. The samples have direct bandgap energies of 1.95 eV (x = 0), 2.06 eV (x = 0,2) and 2.1 eV (x = 0,4). These optical results were correlated with the structural analysis by X-Ray diffraction.     

Structural and electronic properties of C3N4−nPn (n=0,1,2,3,4)

First principles electronic structure method based on the density functional theory and the local density approximation is used to investigate the structural and electronic properties of C₃N_4−nP_n (n=0,1,2,3,4). It is found that the N-rich compounds energetically favor structures with sp² bonding, while the pseudocubic structure which is characterized by sp³ bonding is preferred by the P-rich compounds. Even though C₃N₄ is a wide-gap semiconductor, the band gap of C₃N_4−nP_n decreases rapidly when N is gradually substituted with P, and the P-rich compounds are predicted to be metallic or narrow-gap semiconductors.     

Ultraviolet emitting (Y1−xGdx)2O3−δ thin films deposited by radio frequency magnetron sputtering: Combinatorial modeling, synthesis, and rapid characterization

Gadolinium-doped, yttrium oxide thin films have been deposited on silicon (001) substrates by radio-frequency (RF) magnetron reactive sputtering that exhibit cathodoluminescence (CL) at ultraviolet frequencies. The maximum CL brightness occurred at λ314–315 nm characteristic of the ⁶P_3 / 2 → ⁸S (λ = 314 nm) transition observed in Gd-doped, yttrium oxide powders. The radiative recombination takes place at the rare earth activator Gd³⁺ site embedded in the Y₂O_3−δ host; the optical transition resides within the band gap of the Y₂O_3−δ host and the transition observed is characteristic of atomic gadolinium. A combinatorial approach to sputtering was used to deposit a film of variable composition from 1 to 23 at.% Gd in Y₂O_3−δ in order to rapidly discern the composition node of optimal CL brightness. A simulation was created for the purpose of predicting the film combinatorial composition for binary and ternary alloys prior to sputtering experiments in order to facilitate our combinatorial thin film synthesis technique. The model prediction varied from the real experimental composition profile by only 2.2 at.% Gd ± 1.6 at.% proving the predictor as a useful aide to complement combinatorial thin film experiments. A film of composition Y_1.56Gd_0.44O_3.25 (8.3 at.% Gd) yielded the maximum CL brightness. CL brightness increased continuously up to the 8.3 at.% Gd composition due to the increased number of activators present in the host. Beyond this composition the brightness drastically decreased. The oxygen composition in the combinatorial film was strongly dependent on the Gd composition; films were sub-stoichiometric δ > 0 below 6 at.% Gd and was over-stoichiometric δ < 0 beyond this composition.     

La(1−x)SrxCoO3 for thin film thermocouple applications

In this study, the LSCO (lanthanum strontium cobalt oxide) family has been investigated for thin film thermocouple applications. Thin films of La_(1−x)Sr_xCoO₃ (x=0.3,0.5,0.7) were prepared on sapphire substrates by pulsed laser deposition. The films were annealed at different temperatures in air and characterized for phase, composition and microstructure to determine their thermal stability. From the phase and composition analyses, it is clear that as the Sr content in LSCO increases, the thermal stability decreases. Among the three compositions studied, x=0.3 had the best phase and chemical stability, and microstructural properties. It was observed that La_0.7Sr_0.3CoO₃ possesses excellent phase, composition and microstructural stability up to 1273 K. Above 1273 K, however, LSCO decomposes resulting in the loss of cobalt and formation of individual oxide phases. Electrical resistivity and Seebeck coefficients were measured in situ as a function of temperature in air up to 1023 K. The electrical and Seebeck coefficient properties were found to be stable for all the three compositions up to 1023 K and studies indicated that electrical conduction occurs through a small polaron hopping mechanism. In conclusion, LSCO possessed good thermal stability in air up to 1273 K and exhibits excellent potential in thin film thermocouple applications.     

Combinatorial pulsed laser deposition and thermoelectricity of (La1−xCax)VO3 composition-spread films

La_1−xCa_xVO₃ composition-spread film library was fabricated by combinatorial pulsed laser deposition and their thermoelectric properties were evaluated paralelly by the multi-channel probes of Seebeck coefficient and electric conductivity. Concurrent X-ray analysis verified the formation of solid soluted films in the full composition range (0x1) as judged from the linear variation of the lattice constants. The Seebeck coefficients of La_1−xCa_xVO₃ changed from a large negative value to almost zero with the increase of x, due presumably to the variation of valence in vanadium ions.The power factor in this library was as high as 0.6 μW/cm K², which was obtained at x=0, i.e. pure LaVO₃ grown at 800 °C.