Effect of high-energy electron beam irradiation on the properties of AZO thin films prepared by rf magnetron sputtering

We investigated that high-energy electron beam irradiation (HEEBI) performed in air at room temperature affected remarkably the properties of Al-doped ZnO (AZO) films grown on SiO₂ substrates by radio frequency magnetron sputtering techniques. Hall and photoluminescence measurements revealed that the n-type conductivity was preserved in HEEBI treated films with low dose up to 10¹⁵ electrons/cm² and converted to p-type conductivity with further increase in the amount of dose. X-ray photoelectron spectroscopy confirmed the conversion of conductivity by showing that in-diffusion of O₂ from the ambient as well as out-diffusion of Zn from the films took place as a result of HEEBI treatment at high dose of 10¹⁶ electrons/cm². X-ray diffraction analysis indicated that all as-grown films were found to have compressive stress, which was enhanced by HEEBI treatment with the increase of doses. It was also found that worse crystallinity with a smaller grain size was observed in HEEBI treated films with a higher dose, which was correlated with rougher surface morphologies of films observed by an atomic force microscope.     

Effect of film thickness and the presence of surface fluorine on the structure of a thin barrier film deposited from tetrakis-(dimethylamino)-titanium onto a Si(100)-2 × 1 substrate

The structure of a thin film deposited using tetrakis-(dimethylamino)-titanium (Ti(N(CH₃)₂)₄) as a precursor onto a Si(100)-2 × 1 substrate at ultra-high-vacuum conditions was investigated as a function of film thickness for the films of 20 and 145 nm in the presence of surface copper and fluorine produced by in situ dosing of a common copper deposition precursor, (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane), (hfac)Cu(VTMS), and a hydrogenated form of the hfac ligand, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hfacH. A combination of surface, depth-profiling, and microscopy analytical techniques suggests that the structure of the titanium carbonitride film depends profoundly on its thickness. While the composition of the film was relatively constant throughout its whole thickness, the nanometer-scale structure changed from amorphous at the top of a 145-nm-thick film, to having a significant amount of small (∼ 5 nm) crystallites closer to the TiCN/Si interface. These studies also confirmed the absence of microfractures in the film prepared by this approach. The ex situ depth profiling investigation suggested that if (hfac)Cu(VTMS) is deposited on a TiCN-precovered silicon substrate and briefly annealed to 800 K, the film acts as a diffusion barrier for copper, while surface fluorine penetrates the film rather easily, resulting in fluorine that is distributed uniformly throughout the film.     

渐进因子分析法及其在Au/Ni/Si薄膜俄歇深度剖面研究中的应用

将渐进因子分析法应用于俄歇深度剖面的化学态研究。通过对Au／Ni／Si薄膜样品深度剖析过程的渐进因子分析，最终获得了各元素的化学状态和深度分布，并发现Au／Ni／Si样品中Ni／Si界面在室温下已发生反应，生成富Si的NixSi化合物层。样品经真空退火处理后，Ni／Si界面进一步反应生成Ni2Si合金，而原有的NixSi化合物含量相对减少，并向Si基体侧扩展，同时Ni穿透Au膜在样品表面富集。渐进因子分析的结果与XPS分析相一致。     

Formation of amorphous anodic oxide films of controlled composition on aluminium alloys

Binary, non-equilibrium Al-29at%Nb, Al-44at%Ta, Al-19at%Ti, Al-25at%Ti and Al-32at%Zr alloys were prepared by magnetron sputtering and subsequently anodized at high Faradaic efficiency to grow barrier-type anodic films. Examination in the transmission electron microscope revealed amorphous anodic films of relatively uniform compositions across the film thicknesses, except for a layer of relatively pure alumina, of about 5% of the film thickness, present at the film/electrolyte interface of the Al-Ta alloy. The film compositions, from Rutherford backscattering spectroscopy, indicate that the alloy constituents are oxidized in their alloy proportions to form films comprising intimately mixed units of the various oxides, namely alumina, niobia, titania, tantala and zirconia. The films grow by co-operative transport of metal and oxygen ions under the electric field with formation of film material by both migration of metal ions outwards and of oxygen, and possibly hydroxyl, ions inwards. The average migration rates of Al³⁺, Nb⁵⁺, Ti⁴⁺ and Zr⁴⁺ ions are similar, to within 10%, but Ta⁵⁺ ions migrate more slowly than Al³⁺ ions. The results of the study show that a wide range of compositions of amorphous oxide films can be readily formed by anodic oxidation of appropriate alloys, including compositions containing units of normally crystalline anodic oxides, namely TiO₂ and ZrO₂.     

Effect of deposition time on morphology,corrosion resistance and mechanical properties of Ti-containing conversion coatings on zinc

Ti-containing conversion coatings were obtained on zinc electroplated steel. The influence of deposition time on the coatings morphology, chemical composition, corrosion resistance and mechanical properties were studied. Their chemical composition strongly depends on deposition time. As the time increases from 5 s to 300 s, the Ti content decreases and the Si content increases. For the deposition time of 5 s the Si:Ti atomic ratio in the conversion coating is 0.32 and after 300 s it increases to 9.1, which is accompanied by reduction in corrosion resistance. As deposition time increases, the microhardness of the coatings and their wear resistance deteriorate. Corrosion test results show that the coatings can be applied to protect zinc against corrosion.     

Photochemical synthesis and characterization of Bi2S3 nanofibers

Bismuth sulfide (Bi₂S₃) nanofibers have been successfully prepared by a photochemical method from an aqueous solution of bismuth nitrate (Bi(NO₃)₃) and thioacetamide (TAA) in the presence of complexing agents of nitrilotriacetic acid (NTA) at room temperature. It was found that the irradiation time, the pH of the solution, and the species of complexing agents play important roles in the morphology control of the bismuth sulfate (Bi₂S₃) nanomaterials. The nanofibers were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectra (XPS), and UV-Visible absorption spectra (UV-Vis). Probable mechanisms for the photochemical formation of Bi₂S₃ nanofibers in aqueous solutions are proposed. The photochemical method is a convenient approach for controlling the shape for other metal sulfide semiconductor nanocrystals.     

The formation of a SiOx interfacial layer on low-k SiOCH materials fabricated in ULSI application

The characterizations of SiOCH films using oxygen plasma treatment depends linearly on the O₂/CO flow rate ratio. According to the results of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses, it was found that the carbon composition decreases with increasing O₂/CO flow rate ratio, because more carbon in the Si–O–C and Si–CH₃ bonds on the film surface would be converted by oxygen radicals. It was believed that the oxygen plasma could oxidize the SiOCH films and form a SiO_x interfacial capping layer without much porosity. Moreover, the result of FTIR analysis revealed that there was no water absorbed on the film. A SiO₂-like capping layer formed at the SiOCH film by the O₂/CO flow rate ratio of 0.75 had nearly the same dielectric properties from the result of capacitance–voltage (C–V) measurement in our research.     

Light‐Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid–Liquid Interface

The use of a bottom‐up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light‐responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans‐to‐cis photoisomerization of a photoswitchable metallopolymer that self‐assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans‐azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans‐based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive “smart” surfaces organized with an atomic precision.     

Characterization of magnetic domain walls using electron magnetic chiral dichroism

Domain walls and spin states of permalloy were investigated by electron magnetic chiral dichroism (EMCD) technique in Lorentz imaging mode using a JEM-2100F transmission electron microscope. EMCD signals from both Fe and Ni L_3,2 edges were detected from the Bloch lines but not from the adjacent main wall. The magnetic polarity orientation of the circular Bloch line is opposite to that of the cross Bloch line. The orientations of Fe and Ni spins are parallel rather than antiparallel, both at the cross Bloch line and circular Bloch line.     

电子强关联对LaMnO_3电子结构的影响

本文利用密度泛函对LaMnO3的电子结构进行了计算。结果表明,LaMnO3反铁磁绝缘基态的形成主要依赖于Jahn-Teller畸变而不是电子强关联,但电子强关联效应对LaMnO3电子结构的影响巨大。为了获得正确的结果,本文计算时考虑了适当的电子强关联修正。通过分析比较,表明在位的库仑能U取3.5eV是一个合理的选择。     

Fabrication of gradient material by electron beam smelting based on scanning track control

A new electron beam (EB) control system was developed in a general vacuum EB machine by equipping it with an industrial control computer, programmable logic control (PLC), deflection coil, data acquisition card, power amplifier, etc. In this control system, the scanning track and energy distribution of the EB could be edited off-line, adjusted in real-time, and controlled on-line. Ti-Mo gradient material (GM) with high temperature resistance was fabricated using electron beam smelting (EBS) control. The smelting pro cesses include three steps such as preheating, smelting, and homogenizing. The results show that GM prepared by using smelting technology has fine appearance, and has good integrated interface with Ti alloy. The Mo and Ti elements are gradual diversification in the interface of the gradient material. The microstructure near the Ti alloy base metal is α+β basket-waver grain, and the microstructure near GM is single phase of β solid solution.     

Spatially Resolved Analytical Electron Microscopy at Grain Boundaries of а-Al2O3

In this work the electronic structure and the impurity excess of the basal and rhombohedral twin grain boundaries are investigated, using electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDXS).The measurability of electronic structures of the twin grain boundaries are discussed by comparing theoretical density of states (DOS) from bulk material with interfacial DOS, obtained from local density functional theory (LDFT)calculations.     

Complex investigation of electronic structure transformations in Lead Sulphide nanoparticles using a set of electron spectroscopy techniques

It has been reported recently that kinetic energy of photoelectrons emitted from core levels decreases with decreasing of the nanocrystal size. This phenomenon is called the size shift. The size shift value is the same for donor and acceptor in the compound. The present work is aimed on the explanation of this phenomenon. Crystals of lead sulfide PbS with different size from 50 to 350 nm were grown by chemical bath deposition (CBD) technique from alkaline solution onto Si and GaAs substrates. The morphology and size of crystals were analyzed by high resolution scanning electron microscopy (HRSEM). Complex electron spectroscopy investigations of electronic structure were carried out. In recent experiments X-ray photoelectron spectroscopy (XPS) was used for determination of Pb 4f, and S 2p electronic level positions and their size shifts. To explain the observed dependences in this work, we applied the following methods: analysis of PbS valence band (VB) and Pb 5d electronic level structure in the range ∼0-30 eV by XPS, high resolution electron energy losses spectroscopy (HREELS) for analysis of band gap transformations and work function measurements by Kelvin probe microscopy for the contact potential difference (CPD). The influence of work function increasing, widening of the band gap, transformations in VB and inter-level energy distances with decreasing of nanocrystal size on the size shift function ΔE(R) is discussed.     

Scanning transmission electron microscopy (STEM)-transmission electron microscopy (TEM) analysis of nitrogen ion implanted austenitic 302 stainless steel

The microstructure of nitrogen implanted AISI 302 austenitic stainless steel and the effect of long-term room temperature ageing on it have been studied. Samples were implanted in 1992 with 2.5×10²¹ N₂⁺ m⁻² at 130 keV. The characteristics of the implanted layer and the depth profile have been investigated by scanning transmission electron microscope combined with energy dispersive X-ray spectrometry. Electron diffraction patterns recorded in the implanted layer using transmission electron microscopy confirm the formation of CrN along with the presence of Cr₂N. The identification of phases by glancing angle X-ray diffraction also indicates the formation of Cr₂N and nitrogen solid solutions. The effects of ageing on the microstructure are observed to be small.     

Effect of annealing on diamond-like carbon characteristics by electron spin resonance spectral analysis

We have examined the effect of annealing on physicochemical properties of the diamond-like carbon (DLC) films to produce higher quality films by the electron spin resonance spectral analyses of the immobilized dangling-bond sites (DBS), since amount of DBS reflects the characteristics of DLC films. On heat treatment of DLC deposited from ethylene monomer under anaerobic condition, the DBS decay was clearly shown, as the temperature raised. The decay described by second-order kinetics indicated that the recombination reaction of DBS progressed on heat treatment, suggesting that annealing treatment would accelerate the carbon-carbon covalent bonding network to produce harder films. In fact, the resulted DLC film derived from ethylene monomer showed non-existence of any type of oxygen atom based on X-ray photoelectron spectrum measurement, and water contact angle measurement showed higher hydrophobic surface of the DLC films.     

Ni定位掺杂4H-SiC(001)磁性与光学性质的研究

采用基于密度泛函理论的第一性原理研究了4H-SiC(001)定位掺杂Ni的磁性,结果表明相对于掺杂前表面悬挂键的存在使体系具有弱磁性,Ni定位取代Si位置后得到的体系更加稳定。对比分析了Ni定位取代不同数量的C与Si原子后,得出取代C原子比取代Si原子得到的磁矩大,而且奇数倍的取代较偶数倍取代得到的磁矩大。定位取代一个C与一个Si比单独取代一种原子得到的磁矩大,因此从稳定性与磁性方面考虑C与Si同时取代是最好的掺杂选择。在导电性方面,随着Ni掺杂原子数量增加光电导相应增加。     

用密度泛函理论研究汞在CeO_2(111)表面的吸附

采用密度泛函理论计算了Hg、HgCl、HgCl_2在CeO_2(111)表面的吸附构型、吸附能和态密度。结果表明,Hg在CeO_2(111)表面属于弱化学吸附。HgCl与CeO_2(111)表面为强化学吸附,是反应的重要中间体。HgCl_2在CeO_2(111)表面是物理吸附,易发生解离,脱除。氯对于汞的吸附和氧化产生较强的影响,这与实验结果相一致。基于计算结果,得到汞在CeO_2(111)表面的反应机理。     

Effect of Annealing on the Optical Properties of GaN Films Grown by Pulsed Laser Deposition

In the present study,gallium nitride thin films were grown by using pulsed laser deposition.After the growth samples were annealed at 400 and 600℃in the nitrogen atmosphere.Surface morphology of the as-grown and annealed samples was observed by atomic force microscopy.Post-growth annealing results in an improved surface roughness of the films.Chemical analysis of the samples was performed by X-ray photoelectron spectroscopy.Stoichiometric gallium nitride thin films were obtained for the samples annealed at 600℃.Optical measurements of the samples were performed to measure the band gap and optical constants of the films.Effect of annealing on the band gap and optical constants of the films was studied.     

Characterization by optical emission spectroscopy of an oxygen plasma used for improving PET wettability

Polymers have excellent bulk physical and chemical properties but usually poor surface properties. For wettability improvement plasma technology is one of the most promising techniques. Several studies about surface modifications of polyethylene terephthalate (PET) exposed to an oxygen plasma have been already carried out. In this work an analysis of the plasma phase by optical emission spectroscopy (OES) has been employed in order to establish a correlation with the surface effects induced by plasma exposition on PET chemical composition and wettability, investigated by X-ray photoelectron spectroscopy (XPS) and water contact angle measurements, respectively. The treatment has been carried out for a time of 60 s at a constant pressure (15 Pa) and at different process powers ranging from 20 to 200 W. As expected, the best performance has been obtained at a power of 200 W due to the larger presence of oxygen radicals (OI) with the assistance of ionic species (OII, O₂⁺) which create dangling bonds on the substrate surface.