Growth and characterization of tetragonal bismuth ferrite–lead titanate thin films

Thin films of tetragonal bismuth ferrite–lead titanate (1 − x)BiFeO₃–xPbTiO₃ with x = 0.9–0.7 were prepared by pulsed laser deposition (PLD). The films exhibit a dense columnar grain growth. XRD analysis reveals that the films have a perovskite structure and exhibit a preferred (1 1 1) texture. The film microstructure was studied using SEM. The ferroelectric properties of the films are discussed in the light of polarization-field hysteresis behaviour and impedance spectroscopy. The remanent polarization values ranged between 2P_r  45 and 60 μC cm⁻² at a field amplitude of 500 kV cm⁻¹ and −10 °C, while the dielectric permittivity of the films ranged between 375 and 1096 at a frequency of 2 kHz.     

Effect of addition of Cu into ZrOx film on its properties

The article reports on the effect of addition of Cu into the ZrO₂ film on its structure, physical and mechanical properties. The ZrO₂ and Zr–Cu–O films were reactively sputtered using a dc unbalanced magnetron from Zr (99.9) and ZrCu (90/10 at.%) targets in Ar + O₂ mixture at the substrate temperature T_s = 300, 400 and 550 °C and total sputtering gas pressure p_T = 1 Pa on steel, Si(100) and glass substrates. The structure of films was characterized by an X-ray diffraction (XRD) and mechanical properties, i.e. microhardness H, effective Young's modulus E* = E / (1 − ν²) and elastic recovery W_e, were measured using a microhardness tester; E and ν are the Young's modulus and the Poisson ratio, respectively. The film brittleness was characterized by the formation of cracks during the diamond indenter impression into it. 5 μm thick ZrO₂ films prepared in the oxide mode of sputtering are crystalline (m-ZrO₂) and exhibit relatively (i) high hardness H≈16 GPa and (ii) low ratio H³ / E*²≈0.11 GPa. The Zr–Cu–O films with low (≤ 2 at.%) Cu content exhibit (i) crystalline structure, (ii) higher H, (iii) lower (− 1.5 GPa) macrostress σ and (iv) higher ratio H³ / E*²≈0.14 GPa. On the contrary, the Zr–Cu–O films with high (24 to 44 at.%) Cu content exhibit (i) X-ray amorphous structure, (ii) lower H≈11 GPa and lower ratio H³ / E*²≈0.075 GPa. A special attention was devoted to the investigation of cracking of Zr–Cu–O films under high (0.5 and 1 N) loads of the diamond indenter. The relations between the film cracking and properties of the film and the substrate were used to assess the toughness of the Zr–Cu–O film. It was found that the film toughness increase with increasing H³ / E*² ratio. It was shown that the addition of Cu to ZrO₂ film can improve its toughness.     

Influence of Al- and Cu-doping on the thermodynamic properties of the LaNiIn–H system

The Pressure–Composition–Temperature (P–C–T) relations for the LaNiIn, LaNi_0.95Cu_0.05In and LaNiIn_0.98Al_0.02–H systems were measured by a volumetric Sieverts’ method at 398–423 K. All isotherms show plateau pressure regions indicating equilibria between two hydride phases. The replacements of Ni by Cu and In by Al affect the P–C–T diagrams, stability of the hydrides, homogeneity regions of the hydrides formed, slope of the isotherms and critical temperatures of the β–γ transition. In addition, the Cu-doping induces a significant hysteresis between the hydrogen absorption and desorption processes. The relative partial molar thermodynamic properties for the studied systems are: ΔH_H = −34.6 ± 2.1 kJ (mol_H)⁻¹, ΔS_H = −70.7 ± 3.6 J (K·mol_H)⁻¹ for LaNiIn–H; ΔH_H = −34.1 ± 0.5 kJ (mol_H)⁻¹, ΔS_H = −74.9 ± 1.0 J (K·mol_H)⁻¹ for LaNi_0.95Cu_0.05In–H; ΔH_H = −33.2 ± 0.8 kJ (mol_H)⁻¹, ΔS_H = −68.3 ± 1.2 J(K·mol_H)⁻¹ for LaNiIn_0.98Al_0.02–H.     

Barrier and porous anodic oxides on InSb

Anodizing of InSb at 5 mA cm⁻² in sodium tungstate electrolyte is shown to produce barrier-type amorphous oxide at relatively low voltages, to about 40 V, and porous-type amorphous oxide at increased voltages. The barrier-type amorphous oxide, consisting of units of In₂O₃ and Sb₂O₃, distributed relatively uniformly throughout the film, develops at a formation ratio of 2.2 ± 0.2 nm V⁻¹. The outer 15–20% of the film also contains tungsten species. The relatively high efficiency of barrier film growth reduces significantly with transition to porous oxide, which is associated additionally with generation of oxygen at the film surface. The final oxide, at 65 V, comprises pores, of typical diameter 80 nm, orientated approximately normal to the substrate and extending from a barrier region to the film surface.     

Raman spectroscopy analysis of polypyrrole films as protective coatings on iron

In situ Raman spectroscopy was used to study the redox modifications of electropolymerized polypyrrole (Ppy) films used as protective coatings on iron. A preliminary study of the redox behavior of Ppy on platinum was carried out for highlighting the most sensitive bands to potential variations: the 1560–1620 cm⁻¹ as well as the 930 and 980 cm⁻¹ peaks show a strong dependence on the applied potential. In situ Raman spectra of Ppy on iron were recorded at different times after immersion in a 3% NaCl solution. They formally display the same peaks as those found for platinum, allowing to characterize the redox state of the Ppy film at the solution/film interface. Additional ex situ Raman spectra allowed to identify the corrosion products at the Ppy/metal interface. These results complement kinetics analysis early developed to understand the protection mechanism and its loss.     

Optical constants of polyacetylene

Optical constants of neat cis- and trans-(CH)_x and (CD)_x films are determined by measuring infrared, visible and ultraviolet spectra of the film and its thickness directly. The absorption coefficient of cis-(CH)_x at the absorption maximum 18 500 cm⁻¹ was (1.5 ± 0.1) × 10⁵ cm⁻¹ and that of trans-(CH)_x at 15 500 cm⁻¹ was 1.5 × 10⁵ cm⁻¹. The same values as those of (CH)_x were obtained for (CD)_x. The refractive indices and dielectric constants of cis- and trans-(CH)_x were calculated based on absorptionvspectral data.     

Possible methods of recycling NdFeB-type sintered magnets using the HD/degassing process

With the rapid growth in the use of NdFeB-type magnets and with the growing environmental need to conserve both energy and raw materials, the recycling of these magnets is becoming an ever important issue. In this paper it is demonstrated that hydrogen could play a vital role in this process. Fully dense sintered NdFeB-type magnets have been subjected to the hydrogen decrepitation (HD) process. The resultant powder has been subsequently processed in one of two ways in order to produce permanent magnets. Firstly, the powder was subjected to a vacuum degassing treatment over a range of temperatures up to 1000 °C in order to produce powder that would be suitable for the production of anisotropic bonded or hot pressed magnets. Secondly, the HD-powder has been used to produce fully dense sintered magnets; in which case optimisation of the milling time, sintering temperature and time was carried out. The optimum degassing temperature for coercive powder was found to be 700 °C, giving powder with a remanence (Br) of 1350 mT (±50 mT) and an intrinsic coercivity (Hcj) of 750 kA m⁻¹ (±50 kA m⁻¹). The best sintered magnet was produced by very lightly milling the powder (30 min, roller ball mill), aligning, pressing and vacuum sintering at 1080 °C for 1 h. The magnetic properties of this magnet were: (BH)_max = 290 kJ m⁻³ (±5 kJ m⁻³), Br = 1240 mT (±50 mT) and Hcj = 830 kA m⁻¹ (±50 kA m⁻¹); representing decreases of 15%, 10% and 20%, respectively, from the properties of the initial magnet.     

Influences of ion migration and electric field on the layered anodic films on Al–Mg alloys

Anodizing of sputtering-deposited Al–Mg alloys containing 27 and 32 at.% magnesium in sodium hydroxide electrolyte is shown to develop two-layered anodic oxide films. The outer layer contains aluminium and magnesium species, and is enriched in the latter species relative to the alloy, particularly towards the film surface. The inner layer also contains the two alloy species but is depleted in magnesium, due to Mg²⁺ ions migrating to the outer layer faster than Al³⁺ ions. The ratio of the thickness of the outer layer to that of the film increases with increase of magnesium content of the alloy. The presence of aluminium species in the outer layer is attributed to the penetration of the outer layer by oxide of the inner layer with lower ionic resistance. This mechanism of film growth appears to be sustainable to alloy concentrations to 40 at.%Mg, when the inner layer may no longer form. Enrichment of alloying elements can accompany film growth on Al–Mg alloys, as shown by enrichment of tungsten to 2–3 × 10¹⁵ atoms cm⁻² in an Al–26 at.%Mg–1 at.%W alloy.     

Effects of supply time of Ar gas current on structural properties of Au-catalyzed ZnO nanowires on silicon (1 0 0) grown by vapor–liquid–solid process

ZnO nanowires were grown on Au-coated Si (1 0 0) substrates by the method of vapor–liquid–solid (VLS) growth processing technique. The effects of supply time of Ar gas current on morphology and microstructure of Au-catalyzed ZnO nanowires were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. The results showed that the morphologies of ZnO nanostructures strongly depended on the time of flowing Ar gas. When the time of flowing Ar gas was 90 s, ZnO showed nanowires with hexagonal structure. Their diameters and lengths were 160 nm and 20 μm, respectively, on average, and the Raman scattering peak located at 438 cm⁻¹ reached maximum intensity. The results also showed that the ZnO growth could be patterned by controlling the initial position of Au-coated area on the Si substrates.     

Magnetic fluctuation effects on Raman scattering in the organic superconductor κ-ET2Cu[N(CN)2]Br

We present a study of the 503, 880, 890, 901, 920, and 1475 cm⁻¹ Raman active κ-ET₂Cu[N(CN)₂]Br single crystal phonons, around T=40 K, where an anomaly in the longitudinal sound velocity and antiferromagnetic spin fluctuations have been detected. Doublets, narrowing of phonon lines and non-monotonic intensity variations, as a function of temperature, are observed indicating a possible interaction between phonon and correlated electrons.     

Improvement of high-temperature oxidation resistance of TiAl-based alloy by sol–gel method

Lithium lanthanoid silicate, a high temperature lithium ion conducting solid electrolyte, synthesized by sol–gel method, has been characterized by TGA/DTA, XRD, FTIR and SEM. Conductivity was found to be 0.847 × 10⁻⁶ Ω⁻¹ cm⁻¹ at 750 °C and activation energy was 0.5 eV.     

An electrochemical method for the preparation of Mg–Li alloys at low temperature molten salt system

Mg–Li alloys have been prepared by electrolysis in a molten salt electrolyte of 50% LiCl–50% KCl (mass%) at low temperature of 420–510 °C. The effects of electrolytic temperature and cathodic current density on alloy formation rate and current efficiency were studied. For the deposition of metallic lithium on the cathode consisting of solid Mg and liquid Mg–Li, both electrolytic temperature and cathodic current density have no obvious influence on current efficiency; while for the deposition of metallic lithium on the solid magnesium cathode, both electrolytic temperature and cathodic current density greatly affect alloy formation rate and current efficiency. The optimum electrolysis condition is—molten salt mixture, LiCl:KCl = 1:1 (mass%), electrolytic temperature: 480 °C, cathode current density: 1.13 A cm⁻². Mg–Li alloys with low lithium content (about 25 wt% Li) were prepared via electrolysis at low temperature following by thermal treatment at higher temperature.     

Thin film of bis(ethylenedithio)-tetrathiafulvalene radical salt with Dawson polyoxometalate

The thin film of bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF or ET) radical salt with Dawson polyoxometalate [P₂W₁₈O₆₂]⁶⁻ was prepared on gold substrate by using electrochemical process. The film was characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), electron spin resonance spectroscopy (ESR) and cyclic voltammetry (CV). Scanning electron microscope (SEM) micrograph of the film exhibits a smooth and uniform surface layer containing micronic grains. The thickness of the film estimated by SEM is ca. 22 μm. The film exhibits semiconducting behavior with a room-temperature conductivity 6.5 × 10⁻³ S cm⁻¹.     

Role of rf power on the properties of undoped SnOx films deposited by rf-PERTE at low substrate temperature

Transparent and conductive undoped tin oxide (SnO_x) thin films were deposited at low substrate temperature (< 140 °C) by radio frequency (rf) plasma enhanced reactive thermal evaporation (rf-PERTE) of tin (Sn) in the presence of oxygen The undoped SnO_x films were not submitted to any post-annealing treatments. The influence of rf power variation on the optical, electrical and structural properties of the as-grown films is presented. A variation in the films' structure was verified with the increase of rf power. Undoped SnO_x films, 90 nm average thick, deposited at rf power range of 60–70 W are nanocrystalline, show a conductive behaviour, an average visible transmittance of ≥ 80% and a maximum electrical conductivity of about 34.6 (Ω cm)^− 1. Films deposited at lower values of rf power (40 W) are amorphous and exhibit a semiconductive behaviour, showing an electrical conductivity of about 7.54 × 10^− 1 (Ω cm)^− 1. As a low substrate temperature deposition process is used, SnO_x thin films can be obtained on a wide range of substrates.     

Effects of milling, doping and cycling of NaAlH4 studied by vibrational spectroscopy and X-ray diffraction

The effects of milling and doping NaAlH₄ with TiCl₃, TiF₃ and Ti(OBuⁿ)₄, and of cycling doped NaAlH₄ have been investigated by infrared (IR) and Raman spectroscopy and X-ray powder diffraction. Milling and doping produce similar effects. Both decrease the crystal domain size (900 Å for milled and 700 Å for doped, as compared to 1600 Å for unmilled and undoped NaAlH₄) and increase anisotropic strain (by a factor >2.5, mainly along c). They also influence structure parameters such as the axial ratio c/a, cell volume and atomic displacement amplitudes. They show IR line shifts by 15 cm⁻¹ to higher frequencies for the Al–H asymmetric stretching mode ν₃, and by 20 cm⁻¹ to lower frequencies for one part of the H–Al–H asymmetric bending mode ν₄, thus suggesting structural changes in the local environment of the [AlH₄]⁻ units. The broad ν₃ bands become sharpened which suggests a more homogeneous local environment of the [AlH₄]⁻ units, and there appears a new vibration at 710 cm⁻¹. The Raman data show no such effects. Cycling leads to an increase in domain size (1200–1600 Å), IR line shifts similar to doped samples (except for TiF₃: downward shift by 10 cm⁻¹) and a general broadening of the ν₃ mode that depend on the nature of the dopants. These observations support the idea that some Ti diffusion and substitution into the alanate lattice does occur, in particular during cycling, and that this provides the mechanism through which Ti-doping enhances kinetics during re-crystallisation.     

Growth of highly oriented Pt(100) thin films on a MgO(100) seed layer deposited on Si(100) substrates by rf magnetron sputtering

The growth of highly oriented Pt(100) thin films on Si(100) substrates deposited by rf magnetron sputtering was studied using a MgO(100) seed layer. The effects of the sputtering parameters on the growth of the MgO(100) seed layer were investigated in order to obtain the deposition condition which gives the best crystalline quality of (100) oriented MgO thin films. A highly crystallized MgO(100) film was obtained at a substrate temperature of 425°C, a rf power of 4.4W/cm² and a pressure of 12.5 mTorr. The crystalline quality of the MgO film was greatly decreased when the Si substrate was oxidized. The degree of (100) preferred orientation of the Pt film deposited on a MgO(100)//Si(100) substrate was found to be sensitive to the thickness of the MgO(100) seed layer, which is explained by the thickness dependence of the crystalline quality and the surface roughness of the MgO seed layer. A highly oriented Pt(100) film, for which the I₂₀₀/(_I200+I₁₁₁) ratio was about 0.8, was obtained at 550°C on a 50 nm thick MgO seed layer.     

Mg6Ir2H11, a new metal hydride containing saddle-like [IrH4] and square-pyramidal [IrH5] hydrido complexes

Mg₆Ir₂H₁₁ has been synthesised by both hydrogenation of the intermetallic compound Mg₃Ir at 20 bar and 300 °C, and sintering of the elements at 500 °C under 50 bar hydrogen pressure. Neutron powder diffraction on the deuteride indicates a monoclinic structure (space group P2₁/c, Mg₆Ir₂D₁₁: a=10.226(1), b=19.234(2), c=8.3345(9) Å, β=91.00(1)°, T=20 °C) that is closely related to orthorhombic Mg₆Co₂H₁₁. It contains a square-pyramidal [IrH₅]⁴⁻ complex and three saddle-like [IrH₄]⁵⁻ complexes of which one is ordered and two are disordered. Five hydride anions H⁻ are exclusively bonded to magnesium. The compound has a red colour, is presumably non-metallic and decomposes under 3 bar argon at 500 °C into Mg₃Ir, iridium and a previously unreported intermetallic compound of composition Mg₅Ir₂.     

Resonant Raman scattering study of undoped fullerene thin films

Raman spectra of the fullerenes C₆₀ and C₇₀ have been measured for photon energies from 2.1 to 3.6 eV. Resonant enhancement of the Raman cross section versus wavelength has been measured for the 270, 497, 1424, 1469, and 1568 cm⁻¹ lines, with the diamond 1332 cm⁻¹ line as a reference. A prominent enhancement occurs near 2.4 and 2.5 eV for the C₆₀ 497 cm⁻¹ and 1469 cm⁻¹ lines, respectively. The C₇₀ 1424 cm⁻¹ and 1568 cm⁻¹ lines increase monotonically in intensity between 2.3 and 2.7 eV. The 270 cm⁻¹ line, which has contributions from both C₆₀ and C₇₀, exhibits resonance enhancement which is qualitatively similar to that of the C₇₀ lines. All of the lines show resonance enhancement at 3.4 and 3.5 eV.     

Magnetic structures of Zr6CoAs2-type Ho6−xErxMnBi2 solid solutions

Investigations were made by neutron diffraction on Zr₆CoAs₂-type (space group no. 189) Ho_6−xEr_xMnBi₂ solid solutions. The ferromagnetic ordering temperature decreases from Ho₆MnBi₂ (T_C = 200(6) K) to Er₆MnBi₂ (T_C = 100(4) K), whereas temperatures of ferrimagnetic (or antiferrimagnetic) ordering (T_Ferri and T_AFerri) are found to have non-monotonic dependences on the content of Er: T_Ferri = 58(4) K for Ho₆MnBi₂, T_Ferri = 162(4) K for Ho_4.5Er_1.5MnBi₂, T_Ferri = 150(4) K for Ho₃Er₃MnBi₂, T_AFerri = 78(4) K for Ho_1.5Er_4.5MnBi₂ and T_AFerri = 52(4) K for Er₆MnBi₂.

In these compounds, no local moment was detected on the manganese ion site, except for Ho_1.5Er_4.5MnBi₂ and Er₆MnBi₂ compounds. The manganese magnetic moments (μ_Mn) is 1.5μ_B and these are antiferromagnetically coupled with that of rare earth moments.     

Structural and electrical properties of SrBi2(Ta0.5Nb0.5)2O9 thin films

SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBTN) thin films were obtained by polymeric precursor method on Pt/Ti/SiO₂/Si(1 0 0) substrates. The film is dense and crack-free after annealing at 700 °C for 2 h in static air. Crystallinity and morphological characteristic were examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM). The films displayed rounded grains with a superficial roughness of 3.5 nm. The dielectric permittivity was 122 with loss tangent of 0.040. The remanent polarization (P_r) and coercive field (E_c) were 5.1 μC/cm² and 96 kV/cm, respectively.