A neutron powder diffraction study of the helimagnetic structure of TlCo2Se2−xSx

The magnetic layer structure of TlCo₂Se_2−xS_x has been thoroughly re-investigated with neutron powder diffraction. The cobalt magnetic moments are ferromagnetically arranged within the layers, but the interlayer coupling differs profoundly with varying composition (x): the spins in TlCo₂Se₂ form a helix along the c-axis with a turning-angle of ∼119° at 1.4 K. This kind of helical structure prevails for 0≤x≤1.5 with a gradual decrease of the angle with increasing sulphur content, down to 34°, showing an almost linear relationship with the interlayer distance of Co-Co. For x≥1.75 the interlayer coupling changes to ferromagnetic. Unexpectedly, two helices were found to coexist at x=0.5 and x=1.0. The interaction between adjacent cobalt layers is there characterized by an incommensurate angle (106°, resp., 73°) together with a commensurate angle of 90°. The magnetic structures have been refined as two magnetic phases, each having a characteristic wave vector. A tentative model where the symmetry of the structure and the interlayer distance compete is considered for explaining the simultaneous occurrence of the two kinds of diffraction profile satellites.     

Magnetic and transport property studies of nanocrystalline ZnxFe3−xO4

The magnetic and transport properties of nanocrystalline Zn_xFe_3−xO₄ with x=0.0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, respectively, fabricated by the sol-gel method have been investigated. Large magnetoresistance (MR) was observed and found to be originated both from the tunneling of the spin-polarized electrons across the adjacent ferromagnetic grains and the scattering by the canted spins at the grain surface near the grain boundaries. It has been revealed that the MR for the Zn_xFe_3−xO₄ samples (x=0, 0.5 and 1.0) increases with the temperature decreasing from room temperature until a maximum is reached at around 55 K. Then a sharp drop occurs with the further decrease in temperature, regarded as a spin (cluster) glass transition. For the samples studied, a biggest low field (0.5 T) MR value of about 20% for x=0 at 55 K has been obtained. The mechanism of the MR behavior of the materials was discussed.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Magnetic entropy change in GdCo13−xSix intermetallic compounds

The magnetic entropy change in GdCo_13−xSi_x (x=3.8, 4, 4.1, and 4.2) intermetallic compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. It was found that the magnetic ordering temperatures decrease from 60 K at x=3.8 to 28 K for x=4.2. The magnetic entropy change is calculated from isothermal magnetization versus magnetic field at various temperatures using the Maxwell relation. As a result, the maximum magnetic entropy changes of the investigated compounds, at their Curie temperatures, decrease from 11.5 J/kg K for x=4.2 to 6.86 J/kg K for x=3.8 in a field change of 0-3 T, whereas it decreases from 5.13 J/kg K for x=4.2 to 2.60 J/kg K for x=3.8 in a field change of 0-1 T. Moreover, the maximum value of the magnetic entropy change obtained at a higher field for GdCo_13−xSi_x with x=4 (23.75 J/kg K at 5 T) is comparable to that of various types of compounds with a cubic NaZn₁₃-type structure. Finally, the maximum of the magnetic entropy change is found to decrease with increasing Si content.     

Structural and electrical characterization of SxSe100−x thin films

Thin films of samples of the glassy S_xSe_100−x system with 0 ≤ x ≤ 7.28 have been prepared by thermal evaporation technique at room temperature (300 K). X-ray investigations show that the structure of pure selenium (Se) does change seriously by the addition of small amount of sulphur S ≤7.28%. The lattice parameters were determined as a function of sulphur content. Results of differential thermal analysis (DTA) of the glassy compositions of the system S_xSe_100−x were discussed. The characteristic temperatures (T_g, T_c and T_m) were evaluated. Dark electrical resistivities, ρ, of S_xSe_100−x thin films with different thicknesses from 100 to 500 nm, were measured in the temperature range from 300 to 423 K. Two distinct linear parts with different activation energies were observed. The variation of electrical resistivity of examined compositions has been discussed as a function of the film thickness, temperature and the sulphur content. The application of Mott model for the phonon assisted hopping of small polarons gave the same two activation energies obtained from the resistivity temperature calculations.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.     

Study of polycrystalline bulk CuIn1-xGaxTe2

Polycrystalline CuIn_1−xGa_xTe₂ bulk films were synthesized by reacting, in stoichiometric proportions, high purity Cu, In, Ga and Te in a vacuum sealed quartz ampoule. The phase structure and composition of the bulk films were analysed by X-ray diffraction and energy-dispersive X-ray analysis, respectively. The bulk samples, of p-type conductivity, are found to be near-stoichiometric, polycrystalline, with tetragonal chalcopyrite structure, predominantly oriented along a direction perpendicular to the (1 1 2) plane. Photoluminescence spectra were recorded at 7 K and 700 mW to characterize the defects and the structural quality. The main peak as a function of composition has been studied.     

Near room temperature magnetocaloric properties of melt-spun Gd100−xBx (x=0, 5, 10, 15, and 20 at%) alloys

The magnetocaloric properties of melt-spun Gd-B alloys were examined with the aim to explore their potential application as magnetic refrigerants near room temperature. A series of Gd_100−xB_x (x=0, 5, 10, 15, and 20 at%) alloys were prepared by melt spinning. With the decrease in Gd/B ratio, Curie temperature (T_C) remains constant at ∼293 K, and saturation magnetization, at 275 K, decreases from ∼100 to ∼78 emu/g. Negligible magnetic hysteresis was observed in these alloys. The peak value of magnetic entropy change, (−ΔS_M)_max, decreased from ∼9.9 J/kg K (0-5 T) and ∼5.5 J/kg K (0-2 T) for melt-spun Gd to ∼7.7 J/kg K (0-5 T) and ∼4.0 J/kg K (0-2 T), respectively for melt-spun Gd₈₅B₁₅ and Gd₈₀B₂₀ alloys. Similarly, the refrigeration capacity (q) decreased monotonously from ∼430 J/kg (0-5 T) for melt-spun Gd to ∼330 J/kg (0-5 T) for melt-spun Gd₈₀B₂₀ alloy. The near room temperature magnetocaloric properties of melt-spun Gd_100−xB_x (0≤x≤20) alloys were found to be comparable to few first-order transition based magnetic refrigerants.     

Magnetic properties and room-temperature magnetocaloric effect in the doped antipervoskite compounds Ga1−xAlxCMn3 (0≤x≤0.15)

We report the effects of Al doping on the structure, magnetic properties, and magnetocaloric effect of antiperovskite compounds Ga_1−xAl_xCMn₃ (0≤x≤0.15). Partial substitutions of Al for Ga enhance the Curie temperature (from 250 K for x=0.0 to 312 K for x=0.15) and the saturation magnetization. On increasing the doping level x, the maximum values of the magnetic entropy change (−ΔS_M) decreases while the temperature span of −ΔS_M vs. T plot broadens. Furthermore, the relative cooling power (RCP) is also studied. For 20 kOe, the RCP value tends to saturate at a high doping level (for x=0.12, 119 J/kg at 296 K). However, at 45 kOe, the RCP value increases quickly with increasing x (for x=0.15, 293 J/kg at 312 K). Considering the relatively large RCP and inexpensive raw materials, Ga_1−xAl_xCMn₃ may be alternative candidates for room-temperature magnetic refrigeration.     

Magnetic properties of YFe12−xMox compounds and magnetocaloric effect of YFe9.5Mo2.5

The characterization and magnetic properties of YFe_12−xMo_x (x=2.0, 2.5 and 3.0) with the ThMn₁₂-type structure, and the magnetocaloric effect of YFe_9.5Mo_2.5 were investigated. A directional growth was observed in YFe₁₀Mo₂ alloy. A broad peak in the zero-field-cooling (ZFC) magnetization curve of the YFe_12−xMo_x compounds is ascribed to the existence of ferromagnetic clusters with different site moments and scattered orientations of the moments. The broad range of the peak is reduced with increasing Mo content. A weak peak is observed near 190 K in the ZFC curve of YFe₉Mo₃, which is associated with the 8i sites being mostly occupied by Mo atoms. YFe_9.5Mo_2.5 has a magnetic entropy change of −1.09 J/kg K for a field change of 5 T at 277 K.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Characterization and properties of ZnO1−xSx alloy films fabricated by radio-frequency magnetron sputtering

A series of ZnO_1−xS_x alloy films (0 ≤ x ≤ 1) were grown on quartz substrates by radio-frequency (rf) magnetron sputtering of ZnS ceramic target, using oxygen and argon as working gas. X-ray diffraction measurement shows that the ZnO_1−xS_x films have wurtzite structure with (0 0 2) preferential orientation in O-rich side (0 ≤ x ≤ 0.23) and zinc blende structure with (1 1 1) preferential orientation in S-rich side (0.77 ≤ x ≤ 1). However, when the S content is in the range of 0.23 < x < 0.77, the ZnO_1−xS_x film consists of two phases of wurtzite and zinc blende or amorphous ZnO_1−xS_x phase. The band gap energy of the films shows non-linear dependence on the S content, with an optical bowing parameter of about 2.9 eV. The photoluminescence (PL) measurement reveals that the PL spectrum of the wurtzite ZnO_1−xS_x is dominated by visible band and its PL intensity and intensity ratio of UV to visible band decrease greatly compared with undoped ZnO. All as-grown ZnO_1−xS_x films behave insulating, but show n-type conductivity for w-ZnO_1−xS_x and maintain insulating properties for β-ZnO_1−xS_x after annealed. Mechanisms of effects of S on optical and electrical properties of the ZnO_1−xS_x alloy are discussed in the present work.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.     

Magnetic/structural phase diagram and enhanced giant magnetoresistance in Zn-doped antiperovskite compound Ga1−xZnxCMn3

The structural, magnetic and electrical transport properties of Zn-doped antiperovskite compounds Ga_1−xZn_xCMn₃ (0≤x≤0.30) have been investigated. After partial substitution of Zn for Ga, the Curie temperature increases monotonously and the ground antiferromagnetic (AFM)-ferromagnetic intermediate (FI) phase transition is gradually suppressed. With increasing the doping level x, the saturated magnetizations decreases gradually firstly for x≤0.20, then increases with increasing x. The electrical transport properties of Ga_1−xZn_xCMn₃ are studied at different magnetic fields. Enhanced giant magnetoresistance (GMR) was observed around the AFM-FI transition. With increasing x, the maximal values and peak widths of GMR increase. Particularly, for x=0.20, GMR reaches a maximum value of 75%, spanning a temperature range of 80 K at 50 kOe and displays the behavior of strongly depending on the magnetization history. The possible origins are discussed.     

The effect of addition of gallium on the thermal stability and crystallization kinetic parameters of GaxSe100−x glass system

Differential scanning calorimetry (DSC) technique was used to study the kinetics of amorphous to crystalline transformation for Ga_xSe_100−x glass system (x=0, 2.5 and 5 at%). The kinetic parameters of Ga_xSe_100−x glass system under non-isothermal conditions are analyzed by the model-free and model-fitting models at different constant heating rates (5-50 K/min). A strong heating rate dependence of the effective activation energy of crystallization was observed. The analysis of the present data shows that the effective activation energy of crystallization is not constant but varies with the degree of crystallization and with temperature as well. The crystallization mechanisms examined using the local Avrami exponents indicate that one mechanism (volume nucleation with one-dimensional growth) is responsible for the crystallization process for heating rates 5-50 K/min for Se glass and two mechanisms (volume nucleation with two- and one-dimensional growth) are working simultaneously during the amorphous-crystalline transformation of the Ga_2.5Se_97.5 and Ga₅Se₉₅ glasses (5-50 K/min). The reaction model that may describe crystallization process of all the compositions of Ga_xSe_100−x glass system is Avrami-Erofeev model (g(α)=[−ln(1−α)]^1/n) with n=2 for Se glass. While for Ga_2.5Se_97.5 and Ga₅Se₉₅ glasses, the values of n are equal to 3 and 2 for the heating rates 5-20 and 35-50 K/min, respectively. A good agreement between the experimental and the reconstructed (α-T) curves has been achieved. The transformation from amorphous to crystalline phase in Ga_xSe_100−x glass system demonstrates complex multi-step involving several processes.     

Analysis of magnetic field dependent mobility in ferromagnetic Ga1−xMnxAs layers

The magneto-transport properties of ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fractions in the range of x≈2.2-4.4% were investigated through Hall effect measurements. The magnetic field-dependent Hall mobility for a metallic sample with x≈2.2% in the temperature range of T=0-300 K was analyzed by magnetic field-dependent mobility model including an activation energy of Mn acceptor level. This model provides outstanding fits to the measured data up to T=300 K. It was found that the acceptor levels with activation energies of 112 meV at B=0 Oe decreased to 99 meV at B=5 kOe in the ferromagnetic region. The decrease in acceptor activation energy was due to the spin splitting of the Mn acceptor level in the ferromagnetic region, and was responsible for increase in carrier concentration.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Structural and magnetic properties of MnxCo1−xFe2O4 ferrite nanoparticles

We report on the structural and magnetic properties of nanoparticles of Mn_xCo_1−xFe₂O₄ (x=0.1, 0.5) ferrites produced by the glycothermal reaction. From the analysis of XRD spectra and TEM micrographs, particle sizes of the samples have been found to be about 8 nm (for x=0.1) and 13 nm (for x=0.5). The samples were characterized by DC magnetization in the temperature range 5-380 K and in magnetic fields of up to 40 kOe using a SQUID magnetometer. Mössbauer spectroscopy results show that the sample with higher Mn content has enhanced hyperfine fields after thermal annealing at 700 °C. There is a corresponding small reduction in hyperfine fields for the sample with lower Mn content. The variations of saturation magnetization, remnant magnetization and coercive fields as functions of temperature are also presented. Our results show evidence of superparamagnetic behaviour associated with the nanosized particles. Particle sizes appear to be critical in explaining the observed properties.     

Low-voltage cathodoluminescence property of Li-doped Gd2−xYxO3:Eu

Cathodoluminescent (CL) spectra of Li-doped Gd_2−xY_xO₃:Eu³⁺ solid-solution (0.0?x?0.8) were investigated at low voltages (300 V-1 kV). The CL intensity is maximum for the composition of x=0.2 and gradually reduces with increasing the amount of substituted Y content. In particular, small (∼100 nm) particles of Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ are obtained by firing the citrate precursors at only 650°C for 18 h. Relative red-emission intensity at 300 V of this phosphor is close to 180% in comparison with that of commercial red phosphor Y₂O₃:Eu³⁺. An increase of firing temperature to 900°C results in 400-600 nm sized spherical particles. At low voltages (300-800 V), the CL emission of 100 nm sized particles is much stronger than that of 400-600 nm sized ones. In contrast, the larger particles exhibit the higher CL emission intensity at high voltages (1-10 kV). Taking into consideration small spherical morphology and effective CL emission, Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ appears to be an efficient phosphor material for low voltage field emission display.