The role of grain boundaries in the mechanism of plasma immersion hydrogenation of nanocrystalline magnesium films

In this paper, attention in focused on the nanostructured magnesium films for hydrogen storage. It is shown that 2 μm thick Mg film is transformed into MgH₂ film under high-flux and fluence hydrogen plasma immersion ion implantation at 450 K for 15 min. All hydrogen desorbs at temperature about 530 K, which corresponds to the decomposition of MgH₂ → Mg + H₂↑. The macroscopic and microscopic observations show that magnesium film undergoes a high deformation and restructuring during hydrogenation-dehydrogenation reaction. The suggested hydrogenation model is based upon the incorporation of excess of hydrogen atoms in grain boundaries of nanocrystalline Mg film driven by the increase in surface chemical potential associated with the implantation flux. The results provide new aspects of hydriding of thin nanocrystalline film materials under highly non-equalibrium conditions on the surface.     

Mg nanoparticle switchable mirror films with improved absorption-desorption kinetics

Optical and structural properties of rare-earth free and pure Mg nanoparticle thin film coated with Pd have been investigated. The thickness dependence of the switching properties of magnesium hydride films is presented. We have succeeded to load thin films of Mg to MgH₂ at room temperature and normal pressure of hydrogen gas. In less than 100 s transparent MgH₂ was obtained.     

Hydrogenation of Pd-capped Mg thin films prepared by DC magnetron sputtering

Structural and optical properties of pure Mg thin film coated with Pd have been investigated. Pd-capped Mg thin films had been prepared by DC magnetron sputtering. This work presents an ex situ study on hydrogenation and dehydrogenation kinetics of Pd/Mg films at different conditions using XRD, AFM and optical spectrophotometer. We have succeeded to load thin films of Mg to MgH₂ at normal temperature and normal pressure of hydrogen gas. In hydrogenation, α-MgH₂ phase of magnesium hydride was observed in hydrogenated films at 200 °C and γ-MgH₂ at 250 °C respectively. The desorption kinetics in vacuum also revealed the phase transformation α-MgH₂ to γ-MgH₂. A reflectance change was observed in hydrogenated films in comparison of as deposited thin film. Hydrogenated (H loaded) samples were observed partially transparent in comparison of as deposited.     

Optical switch with low-phase transition temperature based on thin nanocrystalline VOx film

An optical switch is fabricated by using micromachining technology, which is based on thin nanocrystalline vanadium oxide (VO_x) film, and it consists of four layers: a silicon (Si) substrate layer, a VO_x layer, a Si₃N₄ buffer layer, and an aurum (Au) electrode layer. By applying a switching power supply to a pair of the Au electrodes, the optical switch is controlled to exhibit from an “on” state with semi-conducting phase to an “off” state with metallic phase. The optical switch performance is investigated, and testing results show that its extinction ratio is about 14 dB, its switching response time can achieve about 1.5 ms, and the power dissipation required for stimulating switching to work can be below about 15 mW at least, which is lower than the power dissipation of conventional optical switches based on microstructure thin vanadium dioxide (VO₂) films. This kind of optical switch is potential to be applied as optical switch for optical communication.     

High-frequency magnetic properties of soft magnetic cores based on nanocrystalline alloy powder prepared by thermal oxidation

FeSiBNbCu nanocrystalline alloy powder was thermally oxidized in an air atmosphere to enhance an oxide layer formation on the surface of the powder and subsequently toroidal shape FeSiBNbCu nanocrystalline alloy powder cores were prepared by compaction at room temperature. The phase change on the surface of FeSiBNbCu nanocrystalline alloy powder by thermal oxidation was analyzed and its effect on the high frequency magnetic properties of the compacted cores was investigated. By thermal oxidation, the formation of the oxide layer consisting of Fe₂O₃, CuO, and SiO₂ on the surface of FeSiBNbCu nanocrystalline alloy powder was enhanced and the thickness of oxide layer could be controlled by changing the thermal oxidation time. FeSiBNbCu nanocrystalline alloy powder core prepared from the powder treated by thermal oxidation exhibits a stable permeability up to high frequency range over 10 MHz. The core loss could be reduced remarkably and the dc-bias property could be improved significantly, which were due to the formation of oxide layer consisting of Fe₂O₃, CuO, and SiO₂ on the FeSiBNbCu nanocrystalline alloy powder. The improvement in high-frequency magnetic properties of the FeSiBNbCu nanocrystalline alloy powder cores could be attributed to the effective electrical insulation by oxide layer between the FeSiBNbCu nanocrystalline alloy powders.     

Dehydrogenation kinetics of air-exposed MgH2/Mg2Cu and MgH2/MgCu2 studied with in situ X-ray powder diffraction

The dehydrogenation kinetics of air exposed samples of MgH₂/Mg₂Cu and MgH₂/MgCu₂ have been studied with in situ time resolved X-ray powder diffraction. The X-ray setup enabled the recording of full diffraction patterns within 150 s, thereby allowing the study of structural changes combined with simultaneous extraction of kinetic parameters. Phase fractions as a function of time and temperature were derived from series of consecutive diffraction patterns by numerical integration of selected diffraction peaks. The apparent activation energy for the dehydrogenation of the MgH₂/Mg₂Cu, and MgH₂/MgCu₂ sample was found to be 108 kJ/mol and 160 kJ/mol, respectively. Furthermore, substantially improved dehydrogenation kinetics of MgH₂ and resistance towards oxidation of Mg due to the presence of Mg₂Cu/MgCu₂ are discussed in relation to previous work. PACS 61.10.Nz; 81.65.Mq; 82.20.Pm     

Synthesis of basic magnesium carbonate microrods with a “house of cards” surface structure using rod-like particle template

Basic magnesium carbonate (Mg₅(CO₃)₄(OH)₂·4H₂O) microrods with a surface structure of “house of cards” have been synthesized without any alkaline reagent, using rod-like particles, magnesium carbonate trihydrate, as templates. The product was characterized by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). The transformation process from rod-like MgCO₃·3H₂O particles to Mg₅(CO₃)₄(OH)₂·4H₂O microrods with a surface structure of “house of cards” was recorded. Preliminary discussions on possible growth mechanisms of Mg₅(CO₃)₄(OH)₂·4H₂O microrods are also proposed in this paper.     

XPS study of the surface chemistry on AZ31 and AZ91 magnesium alloys in dilute NaCl solution

The surface chemistry on AZ31 and AZ91 magnesium alloys was characterized by X-ray photoelectron spectroscopy (XPS) in the corrosion and the passivation zones. In the corrosion zone, the presence of Mg(OH)₂ and MgCO₃ species was found in the outer surface, whereas, in the inner layer, the co-existence of Mg(OH)₂, MgO and MgCO₃ species was observed for both alloys. The presence of Al³⁺ in the surface electrolyte to form Al₂O₃/Al(OH)₃ and the formation of carbonate product provide a better passivation on the surfaces and retard the chloride-induced corrosion on the materials in the passivation zone.     

A study of interface characteristics in HfAlO/p-Si by deep level transient spectroscopy

Deep level transient spectroscopy (DLTS) and high-frequency capacitance-voltage (HF-CV) measurement are used for the investigation of HfAlO/p-Si interface. The so-called “slow” interface states detected by HF-CV are obtained to be 2.68 × 10¹¹ cm⁻². Combined conventional DLTS with insufficient-filling DLTS (IF-DLTS), the true energy level position of interfacial traps is found to be 0.33 eV above the valance band maximum of silicon, and the density of such “fast” interfacial traps is 1.91 × 10¹² cm⁻² eV⁻¹. The variation of energy level position of such traps with different annealing temperatures indicates the origin of these traps may be the oxide-related traps very close to the HfAlO/Si interface. The interfacial traps’ passivation and depassivation effect of postannealing in forming gas are shown by comparing samples annealed at different temperatures.     

Structural and optical properties of MgxAl1-xHy gradient thin films: a combinatorial approach

The structural, optical and dc electrical properties of Mg_xAl_1-x (0.2≤x≤0.9) gradient thin films covered with Pd/Mg are investigated before and after exposure to hydrogen. We use hydrogenography, a novel high-throughput optical technique, to map simultaneously all the hydride forming compositions and the kinetics thereof in the gradient thin film. Metallic Mg in the Mg_xAl_1-x layer undergoes a metal-to-semiconductor transition and MgH₂ is formed for all Mg fractions x investigated. The presence of an amorphous Mg-Al phase in the thin film phase diagram enhances strongly the kinetics of hydrogenation. In the Al-rich part of the film, a complex H-induced segregation of MgH₂ and Al occurs. This uncommon large-scale segregation is evidenced by metal and hydrogen profiling using Rutherford backscattering spectrometry and resonant nuclear analysis based on the reaction ¹H(¹⁵N,αγ)¹²C. Besides MgH₂, an additional semiconducting phase is found by electrical conductivity measurements around an atomic [Al]/[Mg] ratio of 2 (x=0.33). This suggests that the film is partially transformed into Mg(AlH₄)₂ at around this composition. PACS 78.20.-e; 68.55.-a; 64.75.+g     

Organo-modified magnesium hydroxide nano-needle and its polystyrene nanocomposite

Acrylic acid modified magnesium hydroxide nano-needles (AA–Mg(OH)₂) had been synthesized by alkaline injected into magnesium chloride solution at about 0°C in the presence of acrylic acid (AA). Then the polystyrene/magnesium hydroxide nano-needles composite (PS/Mg(OH)₂) had been prepared by the radical copolymerization with styrene in toluene system using AA–Mg(OH)₂ as a macro-monomer. The elemental analysis (EA) and Fourier transform infrared (FTIR) analyses show that the polystyrene had been grafted onto the surfaces of the nano-needles (AA–Mg(OH)₂). The nano-needles (AA–Mg(OH)₂) had better dispersibility in polystyrene matrix as observed by transmission electron microscope (TEM) analysis. The thermal behavior analysis results from the differential scanning calorimetry (DSC) indicated that the magnesium hydroxide nano-needles had lower thermal decomposition temperature than that of the polymer matrix and it is expected that the nano-needles prepared by the proposed method could be used as an environmental-friendly flame retardant.     

Surface passivation of III-V semiconductors for future CMOS devices—Past research, present status and key issues for future

Currently, III-V metal-insulator-semiconductor field effect transistors (MISFETs) are considered to be promising device candidates for the so-called “More Moore Approach” to continue scaling CMOS transistors on the silicon platform. Strong interest also exists in III-V nanowire MISFETs as a possible candidate for a “Beyond CMOS”-type device. III-V sensors using insulator-semiconductor interfaces are good candidates for “More Moore”-type of devices on the Si platform. The success of these new approaches for future electronics depends on the availability of a surface passivation technology which can realize pinning-free, high-quality interfaces between insulator and III-V semiconductors.This paper reviews the past history, present status and key issues of the research on the surface passivation technology for III-V semiconductors. First, a brief survey of previous research on surface passivation and MISFETs is made, and Fermi level pinning at insulator-semiconductor interface is discussed. Then, a brief review is made on recent approaches of interface control for high-k III-V MIS structures. Subsequently, as an actual example of interface control, latest results on the authors’ surface passivation approach using a silicon interface control layer (Si ICL) are discussed. Finally, a photoluminescence (PL) method to characterize the interface quality is presented as an efficient contactless and non-destructive method which can be applied at each step of interface formation process without fabrication of MIS capacitors and MISFETs.     

Effects of Cl, NO3 and SO4 anions on the anodic behavior of carbon steel in deaerated 0.50 M NaHCO3 solutions

The effects of Cl⁻, NO₃⁻ and SO₄²⁻ aggressive anions on the corrosion and passivation behavior of carbon steel electrode in deaerated 0.50 M NaHCO₃ solutions were studied using potentiodynamic anodic polarization and SEM techniques. It was found that the presence of Cl⁻, NO₃⁻ and SO₄²⁻ anions stimulates the anodic dissolution rate in both the active and the pre-passive potential regions. Moreover, significantly great effects were observed in both the passive and the trans-passive potential regions. Pitting corrosion was observed only in the presence of Cl⁻ anions, while the presence of NO₃⁻ and SO₄²⁻ anions facilitate only passivation by oxygen of water without themselves participating in the cathodic process. Also, it was observed that the effect of NO₃⁻ anion, which is a strong oxidizing agent acting “primarily” as stimulator of the cathodic process and then its reaction product acts “indirectly” retarding the anodic process. On the other hand, the effect of SO₄²⁻ anion, which is a non-oxidizing agent, exerts an “indirect” effect on the cathodic reaction increasing its rate and then “directly” influence on the anodic reaction, retarding it.     

Electrical and optical characterization of SiOxNy and SiO2 dielectric layers and rear surface passivation by using SiO2/SiOxNy stack layers with screen printed local Al-BSF for c-Si solar cells

In c-Si solar cells, surface recombination velocity increases as the wafer thickness decreases due to an increase in surface to volume ratio. For high efficiency, in addition to low surface recombination velocity at the rear side, a high internal reflection from the rear surface is also required. The SiO_xN_y film with low absorbance can act as rear surface reflector. In this study, industrially feasible SiO₂/SiO_xN_y stack for rear surface passivation and screen printed local aluminium back surface field were used in the cell structure. A 3 nm thick oxide layer has resulted in low fixed oxide charge density of 1.58 × 10¹¹ cm⁻² without parasitic shunting. The oxide layer capped with SiO_xN_y layer led to surface recombination velocity of 155 cm/s after firing. Using single layer (SiO₂) rear passivation, an efficiency of 18.13% has been obtained with V_oc of 625 mV, J_sc of 36.4 mA/cm² and fill factor of 78.7%. By using double layer (SiO₂/SiO_xN_y stack) passivation at the rear side, an efficiency of 18.59% has been achieved with V_oc of 632 mV, J_sc of 37.6 mA/cm², and fill factor of 78.3%. An improved cell performance was obtained with SiO₂/SiO_xN_y rear stack passivation and local BSF.     

Effects of annealing temperature on the structural and photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol-gel route

Highly transparent nanocrystalline zirconia thin films were prepared by the sol-gel dip coating technique. XRD pattern of ZrO₂ thin film annealed at 400 °C shows the formation of tetragonal phase with a particle size of 13.6 nm. FT-IR spectra reveal the formation of Zr-O-Zr and the reduction of OH and other functional groups as the temperature increases. The transmittance spectra give an average transmittance greater than 80% in the film of thickness 262 nm. Photoluminescence (PL) spectra give intense band at 391 nm and a broad band centered at 300 nm. The increase of PL intensity with elevation of annealing temperature is related to reduction of OH groups, increase in the crystallinity and reduction in the non-radiative related defects. The luminescence dependence on defects in the film makes it suitable for luminescent oxygen-sensor development. The “Red shift” of excitation peak is related to an increase in the oxygen content of films with annealing temperature. The “Blue shift” of PL spectra originates from the change of stress of the film due to lattice distortion. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process.     

Stacking faults and mechanisms strain-induced transformations of hcp metals (Ti,Mg) during mechanical activation in liquid hydrocarbons

The evolution of the structure and substructure of metals Ti and Mg with hexagonal close-packed (hcp) lattice is studied during their mechanical activation in a planetary ball mill in liquid hydrocarbons (toluene, n-heptane) and with additions of carbon materials (graphite, fullerite, nanotubes) by X-ray diffraction, scanning electron microscopy, and chemical analysis. The temperature behavior and hydrogen-accumulating properties of mechanocomposites are studied. During mechanical activation of Ti and Mg, liquid hydrocarbons decay, metastable nanocrystalline titanium carbohydride Ti(C,H) _x and magnesium hydride β-MgH₂ are formed, respectively. The Ti(C,H) _x and MgH₂ formation mechanisms during mechanical activation are deformation ones and are associated with stacking faults accumulation, and the formation of face-centered cubic (fcc) packing of atoms. Metastable Ti(C,H)x decays at a temperature of 550°C, the partial reverse transformation fcc → hcp occurs. The crystalline defect accumulation (nanograin boundaries, stacking faults), hydrocarbon destruction, and mechanocomposite formation leads to the enhancement of subsequent magnesium hydrogenation in the Sieverts reactor.

     

Electrical characterization of MOS memory devices containing metallic nanoparticles and a high-k control oxide layer

We study the electrical characteristics of a MOS structure in which Pt nanoparticles are embedded. This structure has a tunneling oxide of 3.5 nm in thickness (a SiO₂ thermal oxide layer) on top of a Si wafer, and a control oxide of 27 nm (HfO₂ layer deposited by electron gun evaporation). The nanoparticles are deposited on the SiO₂ layer with electron gun evaporation, at room temperature. The electrical study of the structures demonstrates that the “write” process is initiated at low electric fields. This indicates that this type of memory structure can be very promising for the fabrication of high speed MOSFET memory devices with low power consumption. Our charge retention measurements also show promising results.     

Single step thermal decomposition approach to prepare supported γ-Fe2O3 nanoparticles

γ-Fe₂O₃ nanoparticles supported on MgO (macro-crystalline and nanocrystalline) were prepared by an easy single step thermal decomposition method. Thermal decomposition of iron acetylacetonate in diphenyl ether, in the presence of the supports followed by calcination, leads to iron oxide nanoparticles supported on MgO. The X-ray diffraction results indicate the stability of γ-Fe₂O₃ phase on MgO (macro-crystalline and nanocrystalline) up to 1150 °C. The scanning electron microscopy images show that the supported iron oxide nanoparticles are agglomerated while the energy dispersive X-ray analysis indicates the presence of iron, magnesium and oxygen in the samples. Transmission electron microscopy images indicate the presence of smaller γ-Fe₂O₃ nanoparticles on nanocrystalline MgO. The magnetic properties of the supported magnetic nanoparticles at various calcination temperatures (350-1150 °C) were studied using a superconducting quantum interference device which indicates superparamagnetic behavior.     

Mechanically alloyed metal hydride systems

Mechanosynthesis of metal hydrides is a new field in which important progress has been reported. In this paper, we present recent developments in mechanosynthesis of magnesium-based hydrides for storage applications. The effect of intense milling on magnesium and magnesium hydrides is presented. The influence of various additives on hydrogen-sorption properties is discussed with special emphasis on nanocomposite MgH₂+5 at. % V, where hydrogen-storage characteristics, cycling properties and the mechanism of hydrogen desorption are presented. The production of novel nanocrystalline porous structures by mechanical alloying followed by a leaching technique is discussed. Hot ball-milling, as a new method for rapid synthesis of alloys, is also presented. Finally, two other methods of production of metal hydrides are discussed. One is reactive milling where metal hydrides are synthesized by mechanical alloying under hydrogen pressure, while the other is milling elemental hydrides to produce complex hydrides. Received: 15 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Effect of an electrodeposited yttrium containing thin film on the high-temperature oxidation behaviour of TA6V alloy

Thin films containing yttrium were deposited on TA6V substrates by an electrochemical technique, from a hydro-alcoholic solution. After deposition, the samples were thermally treated to transform the deposited compound into yttrium oxide. The influence of the obtained Y₂O₃ coating on the isothermal oxidation behaviour of the titanium alloy was then investigated between 600 and 850 °C, under synthetic air at atmospheric pressure. The classical “reactive element effect” was not observed even if weight gain was decreased during high-temperature oxidation.