Anelastic spectroscopy measurements of nanoscale charge and magnetic structures in cuprates and manganites

Many perovskites and perovskite related materials exhibit electronic phase separation phenomena at nanometer scales, which are thought to concur to important electric and magnetic properties, like high-T_c superconductivity or colossal magnetoresistence (CMR). Recent and new anelastic spectroscopy experiments are presented, which supply information on the dynamics of such inhomogeneities in the superconductors of the La_2−xSr_xCuO₄ (LSCO) family and on the magnetic perovskite La_1−xCa_xMnO₃. In La_2−xSr_xCuO₄, a relaxation process at liquid He temperatures is identified as due to the motion of the hole stripes, acting as walls between antiferromagnetic (AF) domains. Another process is identified as the depinning of these stripes from defects in the disordered phase. In La_1−xCa_xMnO₃ a glassy dynamic response below the ferromagnetic (FM) transition is attributed to the insulating nanodomains coexisting with the ferromagnetic background.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Electronic structure of the ladder-chain compound Sr14−xCaxCu24O41

The electronic structure of the ladder-chain compound Sr_14−xCa_xCu₂₄O₄₁ is studied by ab initio calculations within the local density approximation. The effects of Ca substitution and structure modulation on electronic structure are discussed. It is found that 0.05 holes per copper atom are on the ladder layers for fully substituted compound, Ca₁₄Cu₂₄O₄₁.     

In situ co-precipitation synthesis and photoluminescence of YxGd1−xVO4:Tm microcrystalline phosphors by hybrid precursors

Y_xGd_1−xVO₄:Tm³⁺ (5 mol%) phosphors were prepared by in situ co-precipitation technology with the different content ratio of Y/Gd (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, respectively). During the process, rare earth coordination polymers with o-hydroxylbenzoate were used as precursors, composing with polyethylene glycol (PEG) as dispersing media. After heat-treatment of the resulting multicomponent hybrid precursors at 900 °C, the samples were obtained. SEM indicated the particles present good crystalline state, whose crystalline grain sizes were about 0.2–2 μm. Under the excitation of 257 nm, all the materials show the characteristic emission of Tm³⁺ which is the strong blue emission centered at 475 nm originating from ¹G₄ → ³H₆ of Tm³⁺. Besides this, concentration quenching appears in the system of YVO₄:Tm³⁺ and GdVO₄:Tm³⁺. And when x reaches 0.5, the system of Y_xGd_1−xVO₄:Tm³⁺ shows the strongest blue emission.     

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.     

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.     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Preparation and photoelectrochemical properties of Ti1−xVxO2 solid solution thin film photoelectrodes with gradient bandgap

A design of a gradient bandgap Ti_1−xV_xO₂ thin film electrode for wet-type solar cells is provided. The gradient bandgap film electrodes were prepared by heating stacked layers of varying V/Ti ratios using the sol-gel method. A composition gradient was observed for some of the samples by X-ray photoelectron spectroscopy although it was not very large. For the Ti_1−xV_xO₂ film electrodes, conspicuous visible light photoresponse and photoelectrochemical stability were observed. The photocurrent increased with increasing bias potential. However, the photocurrent onset potentials of the Ti_1−xV_xO₂ film electrodes were more positive than those of TiO₂ film electrodes, probably owing to the high surface state density introduced by the diffusion of vanadium ions.     

Dielectric and piezoelectric properties of sol–gel derived Ca doped PbTiO3

Synthesis of Ca doped PbTiO₃ powder by a chemically derived sol–gel process is described. Crystallization characteristics of different compositions Pb_1−xCa_xTiO₃ (PCT) with varying calcium (Ca) content in the range x = 0–0.45 has been investigated by DTA/TGA, X-ray diffraction and scanning electron microscopy. The crystallization temperature is found to decrease with increasing calcium content. X-ray diffraction reveals a tetragonal structure for PCT compositions with x ≤ 0.35, and a cubic structure for x = 0.45. Dielectric properties on sintered ceramics prepared with fine sol–gel derived powders have been measured. The dielectric constant is found to increase with increasing Ca content, and the dielectric loss decreases continuously. Sol–gel derived Pb_1−xCa_xTiO₃ ceramics with x = 0.45 after poling exhibit infinite electromechanical anisotropy (k_t/k_p) with a high d₃₃ = 80 pC/N, ′ = 298 and low dielectric loss (tan δ = 0.0041).     

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].     

Bulk Si1−xGex single- and poly-crystals: a new prospective material for electronics

Si_1−xGe_x is a prospective material for electronics. This is mostly because Si_1−xGe_x-based technology is close to silicon-based technology, which is advanced, widely applicable, and cheap. The majority of work on this material is devoted to Si_1−xGe_x-based heteroepitaxy, and in particular to the Si_1−xGe_x/Si system; few publications are devoted to bulk single-crystal. Here we focus on some interesting properties of bulk Si_1−xGe_x solid solutions. First, under heat treatment and alpha- and beta-irradiation the efficiency of defect introduction decreases with the increase of Ge composition of the Si_1−xGe_x single-crystal. This is because Ge atoms in a crystal lattice are annihilation centers for primary defects. Hence, this material is more resistant to temperature and radiation than silicon. Second, it is known that, since Z(Ge)Z(Si), the sensitivity of the material to irradiation should increase with the concentration of Ge. We show that Si_1−xGe_x nuclear detectors have efficiency three times higher than silicon detectors. Finally, we note that one of the major problems in materials based on solid solutions is the composition uniformity. Our investigations on the influence of composition fluctuations on material properties have shown that the material has a sufficient uniformity at x<0.1. Such an alloy is a prospective material for electronics.     

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.     

Optical and electrical properties of p-type AgInSnxS2−x (x = 0–0.04) thin films prepared by spray pyrolysis

AgInSn_xS_2−x (x = 0–0.2) polycrystalline thin films were prepared by the spray pyrolysis technique. The samples were deposited on glass substrates at temperatures of 375 and 400 °C from alcoholic solutions comprising silver acetate, indium chloride, thiourea and tin chloride. All deposited films crystallized in the chalcopyrite structure of AgInS₂. A p-type conductivity was detected in the Sn-doped samples deposited at 375 °C, otherwise they are n-type. The optical properties of AgInSn_xS_2−x (x < 0.2) resemble those of chalcopyrite AgInS₂. Low-temperature PL measurements revealed that Sn occupying an S-site could be the responsible defect for the p-type conductivity observed in AgInSn_xS_2−x (x < 2) thin films.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Optical properties and laser performance of neodymium doped fluoroapatites SrxCa5−x(PO4)3F (x = 0, 1, 2, 3, 4, and 5)

Nd doped fluoroapatites Sr_xCa_5−x(PO₄)₃F(S_xC_5−xPF, X = 0, 1, 2, 3, 4, and 5) single crystals have been grown by the Czochralski technique. Their polarized absorption and emission spectra have been recorded at room temperature and used to calculate the absorption and stimulated emission cross sections. Broadening of the absorption and emission bands is observed for Nd³⁺ in the solid solutions SPF-CPF compared to Nd³⁺ in CPF or SPF. 1% Nd:S_xC_5−xPF, X = 0, 2, 3, 4, and 5, laser rods have been tested in a cavity longitudinally pumped by a 1 W AlGaAs laser diode and compared to Nd:YAG and Nd:YVO₄ rods. All fluoroapatites exhibit very good laser performance with low thresholds and high slope efficiencies, higher than in the case of YAG and equal to the YVO₄ samples. The dependance of the laser output power versus the diode temperature has also been measured for all materials. The laser output was found to be as sensitive to the diode temperature fluctuations for fluoroapatites as for YAG.     

Phase formation process of IrxSi1−x thin films Structure and electrical properties

Experimental data on the phase formation process of amorphous Ir_xSi_1−x thin films with 0.30 ≤ x ≤ 0.41 are presented and discussed in relation to electric transport properties. The structure formation process at temperatures from 300 K up to 1223 K was investigated by means of X-ray diffraction. Distinct phases were observed in the final stage in dependence on the initial composition: Ir₃Si₄, Ir₃Si₅, and IrSi₃. An unknown metastable phase was found in films with a silicon concentration of 61 at.% to 64 at.% after annealing above the crystallization temperature T = 970 K. The crystal structure of this phase was determined by the combined use of X-ray diffraction and electron diffraction. It was found to be monoclinic, basic-face centred with lattice constants a = 1.027 nm, b = 0.796 nm, c = 0.609 nm, and γ = 113.7°. Additionally, microstructure and morphology of the films were investigated by transmission electron microscopy (TEM). The annealing process was studied by means of mechanical stress investigations as well as by electrical resistivity and thermopower measurements. Correlations between the structure, the phase formation and the electrical transport behaviour are discussed on the basis of conduction mechanism.     

YNixMn1−xO3 thin films by pulsed laser deposition: Structure and magnetic properties

Highly oriented YNi_xMn_1−xO₃ thin films on SrTiO₃ (100) substrates were achieved by using pulsed laser deposition for x = 0.33 and x = 0.50. We used a combination of X-ray diffraction, scanning electron microscopy, atomic force microscopy, and magnetic-property measurements. The magnetic transition temperatures (T_c) of the as-grown films are higher than the corresponding bulk values (typically 85 K instead of 80 K, for x = 0.5, and 60 K instead of 50 K, for x = 0.33). Our magnetic measurements also suggest a spin-glass characteristic in the x = 0.33 films, while a cluster glasslike behavior is observed for the films with x = 0.5, which is quite different from that of the bulk samples. Finally, the influence of post-deposition heat treatment on the magnetic properties of the as-grown films is discussed.     

Fabrication of a-Si1−xCx:H thin films for solar cells by the Cat-CVD method using a carbon catalyzer

We propose a new approach to fabrication of hydrogenated amorphous silicon carbide (a-Si_1−xC_x:H) thin films for solar cells by the catalytic chemical vapor deposition (Cat-CVD) method using a carbon catalyzer, which is more stable than tungsten or tantalum. It was found that by using the carbon catalyzer, undoped and boron-doped a-Si_1−xC_x:H films were easily obtained from a SiH₄, CH₄ and B₂H₆ mixture without any change in the catalyzer surface, even after deposition for longer than 30 h.     

Epitaxial grown K1−xRbxTiOPO4 films with extremely flat surfaces for waveguiding

We report on epitaxial {1 0 0} K_1−xRb_xTiOPO₄ waveguide films for the visible spectral range grown on KTiOPO₄ substrates by liquid phase epitaxy. Using the m-line technique a refractive index increase of Δn_x≈0.007 and Δn_z≈0.004 for TM and TE polarisation has been determined for a K_0.78Rb_0.22TiOPO₄ film. Optical transmission and nearfield distribution are comparable to conventional ion-exchanged waveguides. Typical attenuation of about 1 dB/cm for both TM and TE polarisation was obtained at λ=532 and 1064 nm. Energy-dispersive X-ray spectrometry reveals solid-solution films with graded rubidium composition profiles. X-ray rocking curve analyses confirm the epitaxial growth process and indicate perfect and relaxed K_1−xRb_xTiOPO₄ films. Atomic force microscopy investigations reveal regular step structures with step heights Δh<1.3 nm resulting in rms-roughness values of ≈0.4 nm.