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.     

High-throughput characterization of BixY3−xFe5O12 combinatorial thin films by magneto-optical imaging technique

Bi_xY_3−xFe₅O₁₂ thin films have been grown on GGG (Gd₃Ga₅O₁₂) (1 1 1) substrates by the combinatorial composition-spread techniques under substrate temperature (T_sub) ranging from 410 to 700 °C and O₂ pressure of 200 mTorr. In order to study the effect of substrates on the deposition of Bi_xY_3−xFe₅O₁₂ thin films, garnet substrates annealed at 1300 °C for 3 h were also used. Magneto-optical properties were characterized by our home-designed magneto-optical imaging system. From the maps of Faraday rotation angle θ_F, it was evident that the Faraday effect appears only when T_sub = 430-630 °C. θ_F reaches to the maximum value (∼6°/μm, λ = 632 nm) at 500 °C, and is proportional to the Bi contents. XRD and EPMA analyses showed that Bi ions are easier to substitute for Y sites and better crystallinity is obtained for annealed substrates than for commercial ones.     

Highly active Ce1−xCuxO2 nanocomposite catalysts for the low temperature oxidation of CO

A series of Ce_1−xCu_xO₂ nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N₂ adsorption, H₂-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce_1−xCu_xO₂ nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce_0.80Cu_0.20O₂ nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10⁻⁴ mmol g⁻¹ s⁻¹ and high turnover frequency of 7.53 × 10⁻² s⁻¹ (1% CO balanced with air at a rate of 40 mL min⁻¹, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce_0.80Cu_0.20O₂ nanocomposite catalyst.     

Conductivity and sintering property of LaNi1 − xFexO3 ceramics prepared by Pechini method

Preparation of LaNi_1 − xFe_xO₃, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi_1 − xFe_xO₃ with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi_1 − xFe_xO₃ with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi_0.6Fe_0.4O₃ showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.     

Effect of annealing temperature on microstructure, hardness and adhesion properties of TiSixNy superhard coatings

A series of TiSi_xN_y superhard coatings with different Si contents were prepared on M42 steel substrates using two Ti and two Si targets by reactive magnetron sputtering at 500 °C. These samples were subsequently vacuum-annealed at 500, 600, 700, 800 and 900 °C, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), microindenter, Rockwell hardness tester and scratch tester were applied to investigate the microstructure, phase configuration, hardness and adhesion properties of as-deposited and annealed samples. The results indicated that there were two bonds, TiN and Si₃N₄, in all presently deposited TiSi_xN_y thin films, that structure was nanocomposite of nanocrystalline (nc-) TiN embedded into amorphous Si₃N₄ matrices. Annealing treatment below 900 °C played a little role in microstructure and hardness of the coatings although it greatly affected those of steel substrates. The film-substrate adhesion strength was slightly increased, followed by an abrupt decrease with increasing annealing temperature. Its value got to the maximum at 600 °C. Annealing had little effect on the friction coefficient with its value varying in the range of 0.39-0.40.     

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.%.     

Formation of α-Si1−xCx:H and nc-SiC films grown by HWCVD under different process pressure

In this work, hydrogenated amorphous silicon carbide (α-Si_1−xC_x:H) and nanocrystalline SiC (nc-SiC) thin films were deposited by hot wire CVD (HWCVD) using SiH₄/C₂H₂/H₂ gas mixtures. It was found that the films prepared under low gas pressure were α-Si_1−xC_x:H and those prepared under high gas pressure were nc-3C-SiC. The α-Si_1−xC_x:H films showed enhanced density of C-H_n and Si-C bonds with increasing C₂H₂ fraction, which induced an increase in optical gap from 1.8 to 3.0 eV. For the deposition process of nc-SiC, the E_g opt of the deposited films varied from 1.9 eV to 2.5 eV as the filament temperature increased from 1700 to 2100 °C. The deposition rate decreased rapidly from 5.74 nm/min to 0.8 nm/min with increasing T_F.     

Fabrication of FeSe1−x superconducting films with bulk properties

We have fabricated high-quality FeSe_1−x superconducting films with a bulk T_c of 11–12 K on different substrates, Al₂O₃(0 0 0 1), SrTiO₃(1 0 0), MgO(1 0 0), and LaAlO₃(1 0 0), by using a pulsed laser deposition technique. All the films were grown at a high substrate temperature of 610 °C, and were preferentially oriented along the (1 0 1) direction, the latter being to be a key to fabricating of FeSe_1−x superconducting thin films with high T_c. According to the energy dispersive spectroscopy data, the Fe:Se composition ratio was 1:0.90 ± 0.02. The FeSe_1−x film grown on a SrTiO₃ substrate showed the best quality with a high upper critical magnetic field [H_c2(0)] of 56 T.     

Phase stability,elastic, electronic,thermal and optical properties of Ti3Al1−xSixC2 (0≤x≤1): First principle study

The structural parameters with stability upon Si incorporation and elastic, electronic, thermodynamic and optical properties of Ti₃Al_1−xSi_xC₂ (0≤x≤1) are investigated systematically by the plane wave pseudopotential method based on the density functional theory (DFT). The increase of some elastic parameters with increasing Si-content renders the alloys to possess higher compressive and tensile strength. The Vickers hardness value obtained with the help of Mulliken population analysis increases as x is increased from 0 to 1. The solid solutions considered are all metallic with valence and conduction bands, which have a mainly Ti 3d character, crossing the Fermi level. The temperature and pressure dependences of bulk modulus, normalized volume, specific heats, thermal expansion coefficient, and Debye temperature are all obtained through the quasi-harmonic Debye model with phononic effects for T=0−1000 K and P=0−50 GPa. The obtained results are compared with other results available. Further an analysis of optical functions for two polarization vectors reveals that the reflectivity is high in the visible–ultraviolet region up to ∼10.5 eV region showing promise as a good coating material.     

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.     

Effect of nitrogen content on the properties of CrNxOyCz coating prepared by DC reactive magnetron sputtering

The CrN_xO_yC_z coatings were deposited by planar DC reactive magnetron sputtering onto AZ31 Mg alloy and high speed tool steel (HSTS) substrates at a substrate temperature of 200 °C. The effect of N₂ content on composition and structure of the CrN_xO_yC_z coatings was investigated. The structure of the CrN_xO_yC_z coatings was analyzed by a glancing angle X-ray diffraction (GXRD). The cross-section morphology and thickness of the CrN_xO_yC_z coatings were checked by a field emission scanning electron microscope (FESEM), and the composition profile and chemical state were carried out by an X-ray photoelectron spectroscopy (XPS). The experimental results showed that the structure and phase composition of the CrN_xO_yC_z coatings depended on N₂ content. The evolution of the structure of CrN_xO_yC_z coatings was consistent with CrN_x-based coatings, and the CrN_xO_yC_z coatings contained Cr₂O₃, CrO₂, CrO, Cr₃C₂, CrN_x (Cr, CrN, Cr₂N), as well as different chromium oxynitride. However, the carbide and oxynitride were oxidized after annealing.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Role of carbon in the formation of hard Ge1−xCx thin films by reactive magnetron sputtering

We have deposited germanium carbide (Ge_1−xC_x) films on Si(1 0 0) substrate via radio-frequency (RF) reactive magnetron sputtering in a CH₄/Ar mixture discharge, and explored the effects of carbon content (x) on the chemical bonding and hardness for the obtained films. We find that x significantly influences the chemical bonding, which leads to a pronounced change in the hardness of the film. To reveal the relationship between the chemical bonding and hardness, first-principles calculations have been carried out. It is shown that as x increases from 0 to 0.33, the fraction of sp³ C-Ge bonds in the film increases at the expense of Ge-Ge bonds, which promotes formation of a strong covalently bonded network, and thus enhances the hardness of the film. However, as x further increases from 0.33 to 0.59, the fraction of sp³ C-Ge bonds in the film gradually reduces, while that of sp³ C-H and graphite-like sp² C-C bonds increases, which damages the compact network structure, resulting in a sharp decrease in the hardness. This investigation suggests that the medium x (0.17<x<0.40) is most favorable to the preparation of hard Ge_1−xC_x films due to the formation of dominant sp³ C-Ge bonds.     

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.     

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.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Short-range order analysis and some physical properties of InxSe1−x glasses

Bulk In_xSe_1−x (with x=5-25 at%) glasses were prepared using the melt-quench technique. Short range order(SRO) was examined by the X-ray diffraction using Cu(k_α) radiation in the wave vector interval 0.28≤k≤6.5 A⁰⁻¹.The SRO parameters have been obtained from the radial distribution function. The inter-atomic distance obtained from the first and second peak are r₁=0.263 and r₂=0.460 nm, which is equivalent In-Se and Se-Se bond length. The fundamental structural unit for the studied glasses is In₂Se₃ pyramid. Using the differential scanning calorimetry (DSC), the crystallization mechanism of In_xSe_1−x chalcogenide glass has been studied. The glass transition activation energy (E_g) is 289±0.3 kj/mol.There is a correlation amongst the glass forming ability, bond strength and the number of lone pair electrons. The utility of the Gibbs-Di Marzio relation was achieved by estimating T_g theoretically.     

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.     

Growth and characterization of polycrystalline Ge1−xCx by reactive pulsed laser deposition

Polycrystalline thin films of Ge-C were grown on Si (1 1 1) substrates by means of reactive pulsed laser deposition with methane pressure of 100 mTorr. Effect substrate temperature, T_s, on C incorporation to substitutional sites (x) in Ge_1−xC_x was investigated systematically by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyzes. The substrate temperatures were ranging from 250 to 400 °C. The substitutional C composition x in the films by XRD were estimated using the Vegard's linear law. The maximum value of x calculated by XRD was 0.032 for T_s of 350 °C. The position of the C 1s peak at 283.4 eV in the XPS spectrum confirmed the germanium-carbon alloys. XRD measurements indicated that x increased with T_s from 250 °C to 350 °C. At T_s = 400 °C, the estimation of x was lowered. However, the C content calculated by XPS analyzes increased with T_s being more these values than substitutional C composition x. XPS and XRD analyzes demonstrate that the remaining C atoms are incorporated to interstitial sites. The use of the T_s plays important roles in the incorporation of substitutional C and in restraining C-cluster formation in the reactive pulsed laser deposition growth of Ge-C/Si.     

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.