The influence of residual gas on boron carbide thin films prepared by magnetron sputtering

Boron carbide (B₄C) thin films were prepared by magnetron sputtering and residual gas impurities in the films were analyzed by X-ray photoelectron spectroscopy. The impurities, mainly oxygen, decrease with improving vacuum. By using argon ion beam etching of the films, the atomic concentration was measured as a function of etching depth. The binding energy spectra were analyzed using wavelet transform and curve fitting, showing that most of the oxygen impurity is in the form of boron oxides, and that the impurities are physically trapped among columnar structures in the film. In order to improve the base vacuum before coating the film, a range of methods were used, including argon gas filling on the target surface and titanium pre-sputtering. The experimental results show that the latter is an efficient and feasible method. Based on the titanium pre-sputtering technology, the optical performance of W/B₄C multilayer was improved so much.     

Transmission electron microscopy observations of CNT morphology before and after heating in vacuum

Heating of multi-walled carbon nanotubes is often required to obtain clean patterns in the field electron emission microscope (FEEM). A transmission electron micrograph study of morphological changes in the cap structure of multi-walled carbon nanotubes due to heating in vacuum is presented. The lack of significant structural change in the cap structure when specimens were heated to 1925 K for 2.5 h determines an upper bound for the diffusivity of multi-walled carbon nanotube surface atoms, of the order of 10⁻¹⁶ cm²/s at 1925 K.     

Local magnetic ordering of Fe impurities in Pd2MnSn

Mössbauer effect of Fe⁵⁷ embedded as very dilute substitutional impurities in Pd₂MnSn was studied. The impurities are seen to replace the three elements in the alloy. Although the Curie temperature of the alloy is 189K, well below the room temperature, the Mössbauer spectrum recorded at room temperature consisted of two distinct 6-finger magnetic hyperfine spectra and a single unsplit line. One of the 6-finger patterns which corresponds to an internal magnetic field ofH _int=?375 kOe is inferred to arise due to local magnetic coupling of the localized magnetic moments of Fe impurities at the Pd sites with those of the 4 Mn first nearest neighbours of the Fe impurities. The other 6-finger pattern which corresponds to an internal magnetic field ofH _int=?335 kOe is inferred to arise due to the local magnetic coupling of the localized magnetic moments of the Fe impurities at the Sn sites with those of the 6 Mn second nearest neighboours of the Fe impurities. The difference in the internal magnetic fields observed at the Pd and Sn sites in the alloy could be understood qualitatively, on the basis of RKKY theory, as arising due to the different conduction electron polarization contributions to the net internal magnetic field at the Fe impurity sites. The results of the measurements suggest that the localized magnetic moments of Fe⁵⁷ impurities at Pd and Sn sites are antiferromagnetically coupled with the moments of their neighbouring Mn atoms.     

杂质对吸附系统O/RhxPt1-x衬底合金(110)表面偏析的影响

构造了考虑吸附与偏析相互作用情况下无序二元合金Rh_xPt_1-x(110)吸附氧表面的原子集团模型,其中O的覆盖度为0.5;构造了考虑杂质Ni,Cu,W对合金可能产生影响的吸附表面原子集团模型,杂质的掺入采用替位式.应用recursion方法计算了合金表面的环境敏感镶嵌能和电子结构.环境敏感镶嵌能计算表明杂质Ni,Ｃu和Ｗ均使O吸附Rh_xPt_1-x(110)合金表面 关键词： 化学吸附 表面偏析 recursion方法 态密度     

Mössbauer and Nuclear orientation study of magnetic atom behaviour in AuFe below the percolation threshold

An⁵⁷Fe Mössbauer study and⁶⁰Co and⁵⁴Mn nuclear orientation (NO) studies of the Au₈₆Fe₁₄ alloy have been performed. A transition to the spin glass state was observed below approximately 50 K. NO of the⁶⁰Co impurity showed absence of the polarization of the⁶⁰Co nuclei. For⁵⁴Mn impurities the dependence of the Mn effective magnetic field on external field andtemperature was found.     

Electrical conductivity of magnesium oxide single crystal below 1200 K

Using 2-, 3- and 4-electrodes configurations the direct current conductivity of MgO single crystals of nominally highest purity (with respect to cation impurities), grown by arc-fusion, was studied in argon or oxygen between 500–1200 K with special reference to both hysteresis effects during heating and cooling cycles and conductivity phenomena which occur underneath the surface in a thin subsurface zone. The samples contained 250–2500 at.-ppm carbon and typically 800 at.-ppm hydrogen.Below 1000 K the low temperature (LT) conductivity mechanism is characterized by an activation energy of 1.1 ± 0.2eV, distinctly lower than that of the high temperature region (HT) approximately 2.4 eV. By annealing at 300 K the LT mechanism progressively builds up and causes a very pronounced conductivity increase between 700–900 K, unaffected or even enhanced by O₂. Above 900 K, O₂ decreases the conductivity.The LT mechanism is proposed to be due to defect electrons on anion sites corresponding to O^? in the O^2? structure which are a consequence of the presence of carbon and hydrogen dissolved in the MgO and formally derived from the dissolution of traces of CO₂ and H₂O [J. Chem. Phys. Solids43, 129 (1982)].The dissolved carbon is known to segregate into the elastically relaxed subsurface zone (J. Chem. Phys. Solids43, 59 1982). The conductivity data suggest that between 700–900 K, defect species of C + 2O^?, the dipolar CO^?₂, which become strongly enriched in the subsurface zone upon annealing at 300 K, dissociate according to the equation CO₂^2?→CO^? + O^?, thus generating the defect electrons responsible for the LT mechanism.     

负离子元素杂质破坏模型

探讨了HfO₂薄膜中负离子元素杂质破坏模型，并得出薄膜中的杂质主要来源于 镀膜材料. 用电子束蒸发方法沉积两种不同Cl元素含量的HfO₂薄膜，测定薄膜 弱吸收和损伤阈值来验证负离子元素破坏模型. 结果表明，随着Cl元素含量的增加薄膜的弱 吸收增加损伤阈值减小. 这主要是因为负离子元素在蒸发过程中形成挥发性的气源中心而产 生缺陷，缺陷在激光辐照过程中又形成吸收中心. 因此负离子元素的存在将加速薄膜的破坏 . 关键词： 负离子元素杂质 缺陷 吸收     

In vitro corrosion behavior of Ti-O film deposited on fluoride-treated Mg-Zn-Y-Nd alloy

In this paper, a new composite coating was fabricated on magnesium alloy by a two-step approach, to improve the corrosion resistance and biocompatibility of Mg-Zn-Y-Nd alloy. First, fluoride conversion layer was synthesized on magnesium alloy surface by immersion treatment in hydrofluoric acid and then, Ti-O film was deposited on the preceding fluoride layer by magnetron sputtering. FE-SEM images revealed a smooth and uniform surface consisting of aggregated nano-particles with average size of 100 nm, and a total coating thickness of ∼1.5 μm, including an outer Ti-O film of ∼250 nm. The surface EDS and XRD data indicated that the composite coating was mainly composed of crystalline magnesium fluoride (MgF₂), and non-crystalline Ti-O. Potentiodynamic polarization tests revealed that the composite coated sample have a corrosion potential (E_corr) of −1.60 V and a corrosion current density (I_corr) of 0.17 μA/cm², which improved by 100 mV and reduced by two orders of magnitude, compared with the sample only coated by Ti-O. EIS results showed a polarization resistance of 3.98 kΩ cm² for the Ti-O coated sample and 0.42 kΩ cm² for the composite coated sample, giving an improvement of about 100 times. After 72 h immersion in SBF, widespread damage and deep corrosion holes were observed on the Ti-O coated sample surface, while the integrity of composite coating remained well after 7 d. In brief, the data suggested that single Ti-O film on degradable magnesium alloys was apt to become failure prematurely in corrosion environment. Ti-O film deposited on fluoride-treated magnesium alloys might potentially meet the requirements for future clinical magnesium alloy stent application.     

Growth of GaN films on CoGa(001): an EELS and AES study

The formation and properties of ultra-thin GaN films were investigated by means of high-resolution electron energy-loss spectroscopy (EELS) and Auger electron spectroscopy (AES). Using the intermetallic alloy CoGa as the substrate material, GaN can be prepared on the (001) surface upon adsorption of ammonia at 80 K and subsequent thermal decomposition. Ultra-thin GaN films were grown by repeated cycles of ammonia adsorption and heating to 650 K. The GaN films show an FK mode at 695 cm⁻¹, in agreement with calculated spectra based on IR parameters. The electronic energy gap is determined to be E_g ≈ 3.5 eV.     

Changes in optical absorption in iron garnet films due to impurity incorporation

The incorporation of impurities in films of Bi-substituted iron garnets grown by liquid phase epitaxy has been studied by successively adding small amounts of SiO₂ and CaCO₃ to the melt before film growth. It is found that very small additions of CaCO₃ to the melt profoundly influences the optical absorption coefficient and the electrical properties. The impurity absorption ofn-type YIG doped with Si⁴⁺ and Pb²⁺ ions is investigated and its wavelength dependence compared to that ofp-type YIG. The optical transitions involved in the impurity absorption of iron garnets are discussed in terms of transition reaction, photon energy and dependence on the impurity concentration. Depending on the photon energy, one or several transitions may give rise to impurity absorption.     

Method for additional purification of the surface of Si(111) single crystal

A method for additional purification of the surface of single crystals of semiconductors is developed, which consists in the preliminary cleaning of samples by thermal heating in combination or without ion etching in ultrahigh vacuum, followed by implantation with low-energy Ba⁺ ions (or ions of other alkaline elements) and their successive removal by brief (1 min) high-temperature (T = 1550 K) thermal heating. The effect of additional purification is achieved by the fact that the embedded ions of Ba⁺ or other alkaline elements, being active, form compounds with impurity atoms (O, C, S, N, etc.) and are removed during hightemperature heating.     

Nb-Al合金高温氧化机理

通过自编软件建立了铝氧化膜与基体铌界面的原子集团模型,用递归法计算了合金的原子埋置能、原子结合能等电子参数,从电子层面分析铌合金高温氧化机理.研究表明:铝通过晶界扩散偏聚在合金表面,并与氧结合生成致密的Al2O3氧化膜,阻挡氧向铌基体扩散.晶界和稀土元素能提高氧化膜与基体间的原子结合能,增加其界面的结合强度,加强氧化膜与基体铌间的黏附性.因此,通过在合金中添加稀土元素或细化合金晶粒均能提高铌合金的抗高温氧化性能.     

Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

The effect of polymer coatings on switching behavior and cycling durability of Pd/Mg-Ni thin films

Although Pd-capped Mg-Ni alloy switchable mirror thin films have potential applications in smart windows and optical switches, they degrade quickly and cannot be switched after about 150 cycles. This must be improved for practical use. In this study, we tested several polymer coatings on the surface of Pd/Mg₄Ni switchable mirror thin films as a protective membrane and evaluated the optical switching property and durability. The polymer membrane is able to suppress the oxidization of Mg because it has an excellent gas separation characteristic. Polymer coating extended the switching durability of samples to about 1000 cycles. In addition, the transmittance of the thin film in the transparent state is improved by the coating.     

Adsorption and solution of H2, D2, N2, O2 and CO by (100) Ta

Sticking coefficients, saturation densities, and solution rates of gases on (100) Ta are obtained by comparing with results on (100) W using Auger electron spectroscopy and flash desorption. Hydrogen has a lower sticking coefficient on (100) Ta than on polycrystalline Ta, but solution occurs readily even at 78°K. Differences between H₂ and D₂ are observed for both adsorption and solution. Nitrogen is confined to the surface of Ta for T < ≈500°K, and adsorbed nitrogen dissolves with an activation energy of ≈2.5 kcal mole^?1 upon heating to higher temperatures. The saturation density of O₂ at 300° K is approximately twice that on (100) W. The first monolayer dissolves at ≈500°K but the second dissolves or desorbs only at much higher temperatures. Carbon monoxide adsorbs without solution of either species at 300°K. At ≈500°K carbon dissolves completely leaving oxygen which desorbs at much higher temperature.     

多层膜外退火方法制备MgB2超导薄膜

报道了利用电子束蒸发的Mg/B多层膜作为前驱体，然后退火制备MgB₂薄膜的工作. 实验中发现，采用翻转膜面的退火处理方式可以有效地避免降温过程中Mg蒸气在薄膜表面形成的颗粒凝结，由此稳定地实现了面积为10 mm×10 mm，均匀、平整的超导薄膜的制备，T_c达35 K，转变宽度为0.8 K，在5 μm×5 μm的区域内薄膜的平均粗糙度小于10 nm. 为了便于后续器件制作过程中的微加工工艺，研究了膜厚小于1000 ?时薄膜的成相规律，发现当样品厚度减薄后，T_c会有明显降低. 通过调整前驱薄膜中的不同分层厚度，仍可实现转变温度达30 K以上、厚度约600 ?的MgB₂薄膜，在20 K时的临界电流密度为2.4×10⁶ A/cm².     

Association energy of divalent and monovalent impurities with edge dislocations in NaCl

In the present paper calculations have been made of the association and interaction elastic energies for monovalent cation impurities and divalent cation impurities unassociated and associated with cation vacancies in the form of dipoles with dislocationsa/2 r _{+ +} < r_{Ca ^{+ +}} r_{ + + }< r_{Ca^{ + + } } in the compressed region of dislocation, mainly on the dislocationa/2110 {100}. In the case of divalent impurities associated with cation vacancies in the form of dipoles the increase in impurity concentration can take place at all impurities as in the above mentioned case and additionally Sr⁺⁺

Synthesis and characterization of pristine Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> and Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for lithium ion batteries

The cathode materials, pristine Li₂MnSiO₄ and carbon-coated Li₂MnSiO₄ (Li₂MnSiO₄/C), were synthesized by the sol–gel method. Power X-ray diffraction and scanning electron microscopy analyses show that the presence of carbon during synthesis can weaken the formation of impurities in the final product and decrease the particle size of the final product. The effects of carbon coating on electrochemical characteristics were investigated by galvanostatic cycling test and electrochemical impedance spectroscopy. The galvanostatic cycling test results indicate that Li₂MnSiO₄/C cathode exhibits better electrochemical performance with an initial discharge capacity of 134.4 mAh g⁻¹ and a capacity retention of 63.9 mAh g⁻¹ after 20 cycles. Electrochemical impedance analyses confirm that carbon coating can increase electronic conductivity, which results in good electrochemical performance of Li₂MnSiO₄/C cathode. The two semicircles and the large arc obtained in this study can be attributed to the migration of lithium ions through the solid electrolyte interphase films, the electronic properties of the material, and the charge transfer step, respectively.     

Hyperfine interactions in 111Cd-doped lutetium sesquioxide

We report here first Perturbed Angular Correlation (PAC) results of the electric field gradient (EFG) characterisation at ¹¹¹Cd impurities located at both non-equivalent cation sites of the bixbyite structure of Lutetium sesquioxide, between room temperature (RT) and 1273 K. The comparison with results coming from a systematic ¹¹¹Cd PAC study in bixbyites and with point-charge model (PCM) predictions shows the presence of a trapped defect at RT in the neighbourhood of the asymmetric cation site, which is completely removed at T > 623 K. The anomalous EFG temperature dependence in Lu₂O₃ can be described in the frame of a “two-state” model with fluctuating interactions, which enables the experimental determination of the acceptor energy level introduced by the Cd impurity in the band-gap of the semiconductor and the estimation of the oxygen vacancy density in the sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Water vapor-induced structure modification of vertically-aligned carbon nanotube arrays and successive thin film coating for enhanced field emission properties

Vertically-aligned carbon nanotubes (VCNTs) are used as electron source in various field emission applications owing to its high aspect ratio, chemical inertness, mechanical strength and electrical conductivity. Here, we demonstrate that surface structure modification along with thin film coating enhances the field emission performance, such as turn-on voltage, emission site density, and stability. In the present study, VCNTs with different heights were grown on silicon wafers by thermal chemical vapor deposition followed by the structure modification of VCNTs using capillarity-driven water vapor condensation. We obtained various surface morphologies by varying the water vapor exposure time and heating temperature. In addition, the structure-modified VCNTs surfaces were coated with W and SiO₂ thin films using electron-beam evaporation. It was observed that W-coated VCNTs with modified surface morphology results in the best field emission performance.