Structural, electronic, thermodynamic and optical properties of SrS1−xOx mixed crystals

The structural, electronic and thermodynamic properties of the SrS_1–xO_x ternary mixed crystals have been studied using the ab initio full potential linearized augmented plane wave (FP-LAPW) method within density functional theory. The effect of composition on lattice parameter, bulk modulus and band gap was investigated. The lattice constants from Vegard's law and the bulk modulus from linear concentration dependence were observed for the alloys. The microscopic origins of the gap bowing were explained by using the approach of Zunger and co-workers. The thermodynamic stability of these alloys was investigated by calculating the excess enthalpy of mixing ΔH_m as well as the phase diagram. In addition to FP-LAPW method, the composition dependence of the refractive index and the dielectric constant was studied by different models.     

The experimental and theoretical investigation of vibration spectra in ferroelectric semiconductor SbSBrxI1−x crystals

The vapor grown SbSBr_xI_1−x (x=0.1; 0.5; 0.9) crystals with clear mirror surfaces have been used for infrared reflection measurements with Fourier spectrometer. The vibration frequencies along c(z)-axis have been derived from Kramers–Kroning and optical parameters fitting analysis of the experimental reflectivity spectra at T=300 K. The theoretical vibration spectra of SbSBr_xS_1−x (x=0.1; 0.5; 0.9) crystals in paraelectric phase (T=300 K) along c(z)-axis have been determined in quasiharmonic approximation by diagonalization of dynamical matrix. The theoretical vibration spectra of these crystals in a–b(x−y) plane have been determined in harmonic approximation. In this work we discuss the nature of anharmonism in SbSBr_xI_1−x crystals along the c(z)-axis.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Conversion of egg shell membrane to inorganic porous CexZr1−xO2 fibrous network

The binary system CeO₂–ZrO₂ is thermally stable and has superior reduction–oxidation properties. It has been commonly used in the three-way catalytic converters for automobiles. In this work, an inorganic biomorphic porous Ce_xZr_1−xO₂ fibrous network was successfully synthesized by using the egg shell membrane (ESM) as templates, and its morphology was a perfect replica of the original ESM. The synthesis involved a simple infiltration and calcination process. A fresh ESM was peeled from a chicken egg shell. It was soaked in a Ce(NO₃)₃ and Zr(NO₃)₄ mixture before it was calcined at 700 °C in ambient environment. The fibers in the biomorphic network had diameter ranged from 1 to 4 μm, and they were composed of Ce_xZr_1−xO₂ nanocrystallites having an average grain size of 10 nm.     

Synthesis, characterization and melt processing of Y1−x(Yb0.9Nd0.1)xBa2Cu3Oz superconductors

Effects of a combined substitute of Yb and Nd on Y site on the superconducting properties of YBa₂Cu₃O_y have been studied. We synthesized Y_1−x(Yb_0.9Nd_0.1)_xBa₂Cu₃O_z compound with x = 0.2, 0.4, 0.6, 0.8 and 1.0. Here, the ratio of Yb–Nd was fixed to be 9:1 for obtaining 123 phase without secondary phases. The melt processing thermal profiles for Y_1−x(Yb_0.9Nd_0.1)_xBa₂Cu₃O_z with x = 0.2 and 0.4 and the addition of 40 mol% {Y_1−x(Yb_0.9Nd_0.1)_x}₂BaCuO₅ and 0.5 wt% Pt in air were determined on the basis of the thermal analysis results. All samples showed a low grain growth rate, particularly for high x values, which may be partially ascribed to un-optimized thermal schedules. Although almost all the samples exhibited low J_c values, the sample with x = 0.2 exhibited T_c of 88.8 K and a relatively high J_c value of 16,000 A/cm² at 77 K for H//c-axis.     

Dispersive optical constants of a-Se100−xSbx films

Thin films of amorphous Se_100−xSb_x (x=5,10 and 20 at%) system are deposited on a silicon substrate at room temperature (300 K) by thermal evaporation technique. The optical constant such as refractive index (n) has been determined by a method based on the envelope curves of the optical transmission spectrum at normal incidence by a Swanpoel method. The oscillator energy (E_o), dispersion energy (E_d) and other parameters have been determined by the Wemple–DiDomenico method. The absorption coefficient (α) has been determined from the reflectivity and transmitivity spectrum in the range 300–2500 nm. The optical-absorption data indicate that the absorption mechanism is a non-direct transition. We found that the optical band gap, E_g^opt, decreases from 1.66±0.01 to 1.35±0.01 eV with increase Sb content.     

Structural and optical properties of Ba(Ti1−x,Nix)O3 thin films prepared by sol–gel process

Ba(Ti_1−x,Ni_x)O₃ thin films were prepared on fused quartz substrates by a sol–gel process. X-ray diffraction and Raman scattering measurements showed that the films are of pseudo-cubic perovskite structure with random orientation and the change of lattice constant caused by Ni-doping with different concentrations is very small. Optical transmittance spectra indicated that Ni-doping has an obvious effect on the energy band structure. The energy gap of Ba(Ti_1−x,Ni_x)O₃ decreased linearly with the increase of Ni concentration. It indicates that the adjusting of band gap can be achieved by controlling the Ni-doping content accurately in Ba(Ti_1−x,Ni_x)O₃ thin films. This has potential application in devices based on ferroelectric thin films.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

Effect of Y2O3 addition on the conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x

The conductivity and elastic modulus of (CeO₂)_1 − x(YO_1.5)_x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y₂O₃; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y₂O₃ dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y₂O₃ dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y₂O₃, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y₂O₃ dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y₂O₃ dopant content of approximately 20 mol%.     

Theoretical investigation of EPR and optical spectra of Mo(V) in [Mo6O19][N(C4H9)4]3 salt

The electron paramagnetic resonance (EPR) spectral data (the g factors and hyperfine structure constants) and d–d transition spectra for the tetragonal Mo⁵⁺ centre in [Mo₆O₁₉][N(C₄H₉)₄]₃ salt are theoretically investigated from the complete diagonalization method (CDM) for a 4d¹ ion in tetragonally compressed octahedron. The theoretical results are in good agreement with the experimental data. The dependency of the g factors of the ground state on the R_∥(MoO bond length) has been studied. It is shown that the g factors varied with the R_∥ approximately in a linear way.     

Growth and properties of air-processed GdBa2Cu3O7−δ superconductors with fined Gd2BaCuO5 and Gd2Ba4CuFeOy additions

We have succeeded in synthesizing a powder form of Gd₂Ba₄CuFeO_y (Gd2411) in air. GdBa₂Cu₃O_7−δ (Gd123)/Gd₂BaCuO₅ (Gd211) precursor powders added with different amounts of Gd₂Ba₄CuFeO_y (x = 0, 0.002, 0.004, 0.02) in molar ratio to Gd123 have been fabricated successfully into the form of large, single grains by the top seeded melt growth (TSMG) process. The relation between the additions amounts of Gd2411/Gd211 and critical current density (J_C) was analyzed. We found Gd2411 particles stably exist in the Gd123 matrix without degradation of superconducting properties owing to the existence of the Fe magnetic ion. The trapped field was observed to increase significantly compared with the bulk without Gd2411 additions.     

Superconductivity in the hole-doped oxy-arsenide RE1−xSrxFeAsO (RE = La, Pr)

Bulk superconductivity was observed in the FeAs-based RE_1−xSr_xFeAsO (RE = La, Pr) when the di-valence element Sr was substituted to the site of the tri-valence element La and Pr. The maximum superconducting transition temperatures T_c for the two systems are 26 K and 16.3 K, respectively. The doping dependence of the electrical properties and structure of these two systems were investigated systematically. A roughly monotonic increase of T_c and the lattice constants (a-axis and c-axis) with Sr concentration and a saturation behavior in the high doping levels were found. We confirmed that conduction in this type of materials is dominated by hole-like charge carriers by the Hall effect measurements. Also the resistive measurements revealed possible higher upper critical field in these systems comparing with the electron-doped ones.     

Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.     

Effect of sintering atmosphere on the electrical and optical properties of (ZnO)1−x(MnO2)x NTCR ceramics

Nominal composition of (ZnO)_1−x(MnO₂)_x (0.005≤x≤0.2) ceramics have been prepared by the standard solid-state reaction method in three different sintering atmospheres: Ar, air, and reductive atmosphere. The effect of sintering atmosphere on the electron spin resonance (ESR), negative temperature coefficient of resistivity (NTCR), and photoluminescence (PL) properties of (ZnO)_1−x(MnO₂)_x ceramics has been investigated in detail. The results demonstrate that the sintering atmosphere has significant effects on the ESR signals of (ZnO)_1−x(MnO₂)_x; the NTCR of the samples sintered in air is larger than those sintering in Ar and reductive atmosphere; the deep-level PL related to oxygen vacancy increases when sintered in the reductive atmosphere.     

Two-fold interferometric measurements of piezo-optic constants: application to β-BaB2O4 crystals

We present the interferometric technique which allows to measure piezooptical and photoelastic characteristics of crystal materials of any symmetry. The offered two-fold interferometric method enables to determine all independent non-zero piezooptic and photoelastic constants by measuring pressure induced changes of optical path. As advantage to known acoustooptical techniques this method allows to measure both the absolute magnitude and sign of photoelastic constants. In general case the determination of 36 components of piezooptic tensor needs to carry out 57 measurements on 16 samples. The corresponding relationships are derived. As an example we apply here the interferometric technique to measure the piezooptic and photoelastic constants in trigonal β-BaB₂O₄ crystals.     

Effect of Ca doping on the superconducting properties of GdBaSrCu3O7−δ bulk samples

Gd_1−xCa_xBaSrCu₃O_7−δ samples (0  x  0.1) were prepared via solid-state reaction. Four-point probes method was used for resistance versus temperature measurements. Results show decrease in T_c by increasing x content. This variation is assumed to be irrelevant to the different phases or impurity effects since X-ray patterns show all samples are tetragonal single-phase. Ca doping decreases the oxygen content and lattice parameters of the samples. It is suggested that Ca prevents the dislocation of oxygen, and then disrupts the hole concentration of the system and antiferromagnetic correlation at CuO₂ planes. Subsequently, destroys the superconductivity of the samples.     

Reduced anti-ferromagnetism promoted by Zn 3d substitution at CuO2 planar sites of Cu0.5Tl0.5Ba2Ca3Cu4O12−δ superconductors

The role of charge carriers in ZnO₂/CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu_4−yZn_yO_12−δ material in bringing about superconductivity has been explained. Due to suppression of anti-ferromagnetic order with Zn 3d¹⁰ (S=0) substitution at Cu 3d⁹ sites in the inner CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu₄O_12−δ superconductor, the distribution of charge carriers becomes homogeneous and optimum, which is evident from the enhanced superconductivity parameters. The decreased c-axis length with the increase of Zn doping improves interlayer coupling and hence the three dimensional (3D) conductivity in the unit cell is enhanced. Also the softening of phonon modes with the increased Zn doping indicates that the electron–phonon interaction has an essential role in the mechanism of high-T_c superconductivity in these compounds.     

Quasi-two-dimensional magnetism in (CnH2n+1NH3)2CuCl4 studied by electron paramagnetic resonance

The quasi-two-dimensional magnetism in the layered transition metal compound (C_nH_2n+1NH₃)₂CuCl₄ (n=10, 14) was investigated by means of electron paramagnetic resonance (EPR) and superconducting quantum interference device measurements. As a result, the high temperature magnetic phase transitions were reflected in the EPR parameters in a sensitive manner.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

Magnetotransport and magnetotunneling in single-layer, two-layer, and three-layer Bi2Sr2Can−1CunOz (n=1,2,3) single crystals

In continuous magnetic fields H up to 28 T, we have studied the out-of-plane transport properties and tunneling characteristics of high-quality nondoped single crystals of the Bi-cuprate family: Bi₂Sr₂CuO_6+δ (Bi2201), Bi₂Sr₂CaCu₂O_8+δ (Bi2212) and Bi₂Sr₂Ca₂Cu₃O_10+δ (Bi2223) grown by an identical method. For all compounds the out-of-plane magnetotransport ρ_c(H) is negative in the temperature region where ρ_c(T) shows in the normal state a semiconducting-like temperature dependence. The negative magnetoresistance of ρ_c corresponds to the suppression of the semiconducting temperature dependence of ρ_c(T) which is found to be isotropic. For the Bi2201 compound, where the normal state can be reached in the available magnetic fields (28 T), a nearly complete suppression of the low-temperature upturn in ρ_c(T) is observed in the highest magnetic fields with a tendency towards a metallic behavior down to the lowest temperatures (0.4 K). Using the break-junction technique, especially for the Bi2212 and Bi2232 compounds, a clear superconducting gap structure can be observed. Both for temperatures above the critical temperature and for magnetic fields above the upper critical field, a pseudogap structure remains present in the tunneling spectra. The applied magnetic fields yield a stronger suppression of the superconducting state compared to that of the normal-state gap structures as manifested in ρ_c(T) transport and tunneling.