Novel 2D self-assembled arrays of SiOx nanowire bundles

Novel 2D ordered arrays formed by self-assembly of SiO_x nanowire bundles have been prepared on a silicon wafer via a facile metal-mediated gas-phase reaction. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Two types of arrays were grown on a substrate surface by adjusting the preparation parameters. The findings suggest that the growth atmosphere, the flow rate of carrier gas and the relative placement of source and substrate are all responsible for the formation of these unique self-assembled structures. The intermolecular action is the internal driving force for the self-assembly. The formation mechanism of the arrays was proposed on the basis of the growing process.     

Deformation behavior of complex carbon nitride and metal nitride based bi-layer coatings

A bi-layer coating consisting of a TiAlCrN inner layer and complex carbon nitride (CN_x) plus CrCN outer layer was deposited on to a high speed steel (M2) substrate via physical vapour deposition (PVD). Detailed microstructural analysis of the coating has been performed via transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XPS analysis indicated that the outer layer contained both C-C bonds, associated with an amorphous phase, and the presence of CrCN, which was confirmed by TEM analysis. Localized deformation of the coating was performed using nanoindentation with a spherical indenter. Force-displacement curves of the indentation tests exhibited a number of ‘pop-ins’ during the loading cycle, indicative of cracking and other deformation events. Cross-sectional analysis of the indents revealed extensive cracking in the TiAlCrN layer and shear steps at the steel-nitride interface, consistent with the events observed in the force-displacement curves. On the other hand minimal cracking was observed in the CN_x + CrCN layer. It is believed that the relatively ductile outer layer inhibits the propagation of cracks from the inner, brittle layer.     

Experimental evolution gone wild

Because of their large population sizes and rapid cell division rates, marine microbes have, or can generate, ample variation to fuel evolution over a few weeks or months, and subsequently have the potential to evolve in response to global change. Here we measure evolution in the marine diatom Skeletonema marinoi evolved in a natural plankton community in CO₂-enriched mesocosms deployed in situ. Mesocosm enclosures are typically used to study how the species composition and biogeochemistry of marine communities respond to environmental shifts, but have not been used for experimental evolution to date. Using this approach, we detect a large evolutionary response to CO₂ enrichment in a focal marine diatom, where population growth rate increased by 1.3-fold in high CO₂-evolved lineages. This study opens an exciting new possibility of carrying out in situ evolution experiments to understand how marine microbial communities evolve in response to environmental change.     

Preparation of nitrogen co-doped SiO2/TiO2 thin films on ceramic with enhanced photocatalytic activity under visible-light irradiation

In this study, we have successfully deposited N-doped SiO₂/TiO₂ thin films on ceramic tile substrates by sol–gel method for auto cleaning purpose. After dip coating and annealing process the film was transparent, smooth and had a strong adhesion on the ceramic tile surface. The synthesised catalysts were then characterised by using several analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM) and UV-vis absorption spectroscopy (UV-vis). The analytical results revealed that the optical response of the synthesised N-doped SiO₂/TiO₂ thin films was shifted from the ultraviolet to the visible light region. The nitrogen substituted some of the lattice oxygen atoms. The surface area of co-doped catalyst increased, and its photocatalytic efficiency was enhanced. The photocatalytic tests indicated that nitrogen co-doped SiO₂/TiO₂ thin films demonstrated higher than of the SiO₂/TiO₂ activity in decolouring of methylene blue under visible light. The enhanced photocatalytic activity was attributed to an increasing of the surface area and a forming of more hydroxyl groups in the doped catalyst.     

Decoration of carbon nanotubes with nearly monodisperse MFe2O4 (MFe2O4, M = Fe, Co, Ni) nanoparticles

Magnetic monodisperse ferrite MFe₂O₄ (M = Fe, Co, Ni) nanoparticles have been successfully deposited on carbon nanotubes (CNTs) by in situ high-temperature hydrolysis and inorganic polymerization of metal salts and CNTs in polyol solution. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectrometry (EDS) and vibrating sample magnetometer (VSM) investigations were used to characterize the final products. The influencing factors for formation of CoFe₂O₄ nanoparticles along CNTs have also been discussed briefly. The main advantage of this synthetic strategy is that it is beneficial for the fabrication of magnetic CNTs with a compact layer of nanoparticles and could be extended to prepare series of ferrite/CNTs nanocomposites via the substitution of metal cations.     

Identifying and rationalizing the morphological,structural, and optical properties of [... formula ...]-Ag2MoO4 microcrystals,and the formation process of Ag nanoparticles on their surfaces: combining experimental data and first-principles calculations

We present a combined theoretical and experimental study on the morphological, structural, and optical properties of β-Ag₂MoO₄ microcrystals. β-Ag₂MoO₄ samples were prepared by a co-precipitation method. The nucleation and formation of Ag nanoparticles on β-Ag₂MoO₄ during electron beam irradiation were also analyzed as a function of electron beam dose. These events were directly monitored in real-time using in situ field emission scanning electron microscopy (FE-SEM). The thermodynamic equilibrium shape of the β-Ag₂MoO₄ crystals was built with low-index surfaces (001), (011), and (111) through a Wulff construction. This shape suggests that the (011) face is the dominating surface in the ideal morphology. A significant increase in the values of the surface energy for the (011) face versus those of the other surfaces was observed, which allowed us to find agreement between the experimental and theoretical morphologies. Our investigation of the different morphologies and structures of the β-Ag₂MoO₄ crystals provided insight into how the crystal morphology can be controlled so that the surface chemistry of β-Ag₂MoO₄ can be tuned for specific applications. The presence of structural disorder in the tetrahedral [MoO₄] and octahedral [AgO₆] clusters, the building blocks of β-Ag₂MoO₄, was used to explain the experimentally measured optical properties.     

Order-disorder transformation in Fe-Pd alloy nanoparticles studied by in situ transmission electron microscopy

We have studied order-disorder transformation in Fe-Pd alloy nanoparticles by in situ transmission electron microscopy (TEM) and electron diffraction. The transformation is size-dependent, and the transformation temperatures are lower than those of the bulk alloys. The transformation proceeds continuously but rather steeply as the temperature increases, which differs from the first-order transformation observed in a bulk alloy or gradual transformation predicted by simulations for nanoparticles. Experimental results indicated that the continuous nature can be attributed to the distribution of the transformation temperature due to the distributions of both particle size and alloy composition. Quantitative intensity analyses of nanobeam electron diffraction (NBD) patterns indicated the existence of short-range order (SRO) inside disordered nanoparticles. The SRO as well as particle size distribution are responsible for the remaining weak superlattice reflections above the transformation temperature. In situ high-resolution TEM (HRTEM) observation revealed the existence of the SRO, which was consistent with the results obtained by NBD. We show that the disorder may not necessarily proceed continuously from the surface toward the center of the nanoparticle. Ordering from the disordered phase upon cooling was also observed by in situ HRTEM, which can be attributed to growth of the SRO.     

Synthesis and electrocatalytic property of mono-dispersed Ag/Fe3O4 composite micro-sphere

One-step reaction was designed to synthesize mono-dispersed Ag/Fe₃O₄ micro-sphere with different Ag content via a facile and easily controlled hydrothermal method without use of any surfactant. The phases and composition analysis of the as-prepared samples were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The morphology of the samples was observed by transmission electron microscopy (TEM) and field-emission scanning electron microscopy (FE-SEM). The results revealed that the Ag/Fe₃O₄ composite samples with different Ag content were micro-spheres with almost the identical size of 175 nm or so in diameter. The electrocatalytic activity of the resultant samples modified on a glassy carbon electrode (GCE) for p-nitrophenol reduction in a basic solution was investigated. The results indicated that all the samples exhibited enhanced electrocatalytic activity for p-nitrophenol reduction, and the sample with 3% Ag exhibited the highest electrocatalytic one.     

Surface wettability of plasma SiOx:H nanocoating-induced endothelial cells' migration and the associated FAK-Rho GTPases signalling pathways

Vascular endothelial cell (EC) adhesion and migration are essential processes in re-endothelialization of implanted biomaterials. There is no clear relationship and mechanism between EC adhesion and migration behaviour on surfaces with varying wettabilities. As model substrates, plasma SiO_x:H nanocoatings with well-controlled surface wettability (with water contact angles in the range of 98.5 ± 2.3° to 26.3 ± 4.0°) were used in this study to investigate the effects of surface wettability on cell adhesion/migration and associated protein expressions in FAK-Rho GTPases signalling pathways. It was found that EC adhesion/migration showed opposite behaviour on the hydrophilic and hydrophobic surfaces (i.e. hydrophobic surfaces promoted EC migration but were anti-adhesions). The number of adherent ECs showed a maximum on hydrophilic surfaces, while cells adhered to hydrophobic surfaces exhibited a tendency for cell migration. The focal adhesion kinase (FAK) inhibitor targeting the Y-397 site of FAK could significantly inhibit cell adhesion/migration, suggesting that EC adhesion and migration on surfaces with different wettabilities involve (p)FAK and its downstream signalling pathways. Western blot results suggested that the FAK-Rho GTPases signalling pathways were correlative to EC migration on hydrophobic plasma SiO_x:H surfaces, but uncertain to hydrophilic surfaces. This work demonstrated that surface wettability could induce cellular behaviours that were associated with different cellular signalling events.     

Optical properties of amorphous, erbium-doped yttrium alumino-borate thin films

In this paper, we report on the optical characterizations of erbium-doped yttrium alumino-borate glassy thin films prepared by the polymeric precursor and sol-gel routes and the spin-coating technique. High quality planar waveguides were produced by a multilayer processing of Y_1−xEr_xAl₃(BO₃)₄ compositions with x = 0.02, 0.05, 0.10, 0.30, and 0.50. Their optical properties were investigated using transmission, photoluminescence, and m-lines spectroscopy, whereas high resolution scanning electron microscopy (HR-SEM) was applied to check film thickness and surface homogeneity. The refractive indices determined from transmission and m-lines spectroscopy are in good agreement just like the film thickness measured by HR-SEM and transmission spectroscopy. We observed low propagation losses, together with efficient photoluminescence emission for polymeric precursor thin films, involving low cost and environment friendly reactants.     

Te concentration dependent photoemission and inverse-photoemission study of FeSe1?xTex

We have characterized the electronic structure of FeSe_1−xTe_x for various x values using soft x-ray photoemission spectroscopy (SXPES), high-resolution photoemission spectroscopy (HRPES) and inverse photoemission spectroscopy (IPES). The SXPES valence band spectral shape shows that the 2 eV feature in FeSe, which was ascribed to the lower Hubbard band in previous theoretical studies, becomes less prominent with increasing x. HRPES exhibits systematic x dependence of the structure near the Fermi level (E_F): its splitting near E_F and filling of the pseudogap in FeSe. IPES shows two features, near E_F and approximately 6 eV above E_F; the former may be related to the Fe 3d states hybridized with chalcogenide p states, while the latter may consist of plane-wave-like and Se d components. In the incident electron energy dependence of IPES, the density of states near E_F for FeSe and FeTe has the Fano lineshape characteristic of resonant behavior. These compounds exhibit different resonance profiles, which may reflect the differences in their electronic structures. By combining the PES and IPES data the on-site Coulomb energy was estimated at 3.5 eV for FeSe.     

Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection

Electrochemical measurements, in situ and ex situ atomic force microscopy (AFM) experiments and infrared reflection absorption spectroscopy (IRAS) analysis were performed to investigate the formation and stability as well as corrosion protection properties of mussel adhesive protein (Mefp-1) films on carbon steel, and the influence of cross-linking by NaIO₄ oxidation. The in situ AFM measurements show flake-like adsorbed protein aggregates in the film formed at pH 9. The ex situ AFM images indicate multilayer-like films and that the film becomes more compact and stable in NaCl solution after the cross-linking. The IRAS results reveal the absorption bands of Mefp-1 on carbon steel before and after NaIO₄ induced oxidation of the pre-adsorbed protein. Within a short exposure time, a certain corrosion protection effect was noted for the pre-formed Mefp-1 film in 0.1 M NaCl solution. Cross-linking the pre-adsorbed film by NaIO₄ oxidation significantly enhanced the protection efficiency by up to 80%.     

Mechanical and environmental properties of Ge1−xCx thin film

Ge_1−xC_x thin film was prepared by plasma-enhanced chemical vapor deposition (PECVD) using GeH₄ and CH₄ as precursors and its mechanical and environmental properties were investigated. The samples were measured by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectrum, FT-IR spectrometer, WS-92 testing apparatus of adhesion and FY-03E testing apparatus of salt and fog. The results show that the infrared refractive index of Ge_1−xC_x thin film varies from 2 to 4 with different x values. The adhesion increases with increasing gas flow ratio of GeH₄/CH₄ and decreases with increasing film thickness. The nanoindentation hardness number decreases with increasing germanium content. Three series films exhibit the best anti-corrosion property when the RF power is about 80 W, or substrate temperature is about 150 °C, or DC bias is about −100 V. Furthermore, increasing the gas flow ratio of GeH₄/CH₄ improves the anti-corrosion property of these films.     

Microstructure of a-plane ZnO grown on LaAlO3 (001)

The microstructure of a-plane ZnO grown on LaAlO₃ (LAO) (001) has been systematically investigated by employing X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Based on the results of XRD and TEM, only a-plane ZnO has been found to grow on LAO (001), and it consists of two types of domains perpendicular to each other. The crystal orientation relationships of a-plane ZnO domains with LAO have been verified to be [0001]_ZnO//[110]_LAO and [11?00]_ZnO//[11?0]_LAO. The domain boundaries in the a-plane ZnO are along the direction in a rotation angle of about 45° from the c-axes of ZnO. The surface morphology of ZnO films in SEM exhibits domain structure in stripe-like shape. The formation of two domains can be attributed to the cubic symmetry of the surface configuration of LAO (001).     

Single cell profiling of surface carbohydrates on Bacillus cereus

Cell surface carbohydrates are important to various bacterial activities and functions. It is well known that different types of Bacillus display heterogeneity of surface carbohydrate compositions, but detection of their presence, quantitation and estimation of variation at the single cell level have not been previously solved. Here, using atomic force microscopy (AFM)-based recognition force mapping coupled with lectin probes, the specific carbohydrate distributions of N-acetylglucosamine and mannose/glucose were detected, mapped and quantified on single B. cereus surfaces at the nanoscale across the entire cell. Further, the changes of the surface carbohydrate compositions from the vegetative cell to spore were shown. These results demonstrate AFM-based ‘recognition force mapping’ as a versatile platform to quantitatively detect and spatially map key bacterial surface biomarkers (such as carbohydrate compositions), and monitor in situ changes in surface biochemical properties during intracellular activities at the single cell level.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Semiconductor-metal phase transition of iron disilicide by laser annealing and its application to form device electrodes

Phase transition of semiconducting β-FeSi₂ to metallic α-FeSi₂ has been realized by laser annealing (Nd:YAG laser, λ=1.064 μm) in order to form ohmic electrodes for β-FeSi₂ devices. The starting samples were 200-nm-thick β-FeSi₂ films formed on Si substrates by reactive deposition epitaxy method. XRD and micro-Raman spectroscopy measurements confirmed the successful phase transition. The electrical resistivity of the α-FeSi₂ film was 2.0×10⁻⁴ Ω·cm, three orders lower than that of the original β-FeSi₂ film (1.4×10⁻¹ Ω·cm). Cross-sectional TEM images and electron diffraction patterns indicated that the upper ∼100 nm of the annealed film was changed to α-FeSi₂ while the lower part remained to be β-FeSi₂. α-FeSi₂ layer had good ohmic contact with β-FeSi₂. A testing p-β-FeSi₂/n-Si diode with laser-annealed α-FeSi₂ as the electrode on β-FeSi₂ showed the same rectifying characteristic as that using Al-evaporated electrode.     

Nanostructural and chemical characterization of supported metal oxide catalysts by aberration corrected analytical electron microscopy

The performance of catalyst materials are usually governed by the precise atomic structure and composition of very specific catalytically active sites. Therefore, structural and chemical characterization at the atomic scale becomes a vital requirement in order to identify any structure-performance relationships existing in heterogeneous catalyst systems. Aberration-corrected scanning transmission electron microscopy (STEM) represents an ideal means to probe the atomic scale structural and chemical information via a combination of various imaging and spectroscopy techniques. In particular, high-angle annular dark-field (HAADF) imaging provides directly interpretable atomic number (Z) contrast information; while X-ray energy dispersive spectroscopy (XEDS) and electron energy-loss spectroscopy (EELS) spectrum imaging can be used to identify the chemical composition and oxidation state. Here we review some applications of aberration-corrected STEM to catalyst research, firstly in the context of supported metal catalysts, which serve as ideal material systems to illustrate the power of these techniques. Then we focus our attention on more recent progress relating to the characterization of supported metal oxide catalysts using aberration-corrected STEM. We demonstrate that it is now possible to directly image supported surface oxide species, study oxide wetting characteristics, identify the catalytic active sites and develop new insights into the structure-activity relationships for complex double supported oxide catalysts. Future possibilities for in situ and gentle low voltage electron microscopy studies of oxide-on-oxide materials are also discussed.     

One-step synthesis and characterization of single Au microballs through self-organization

Uniform single microballs consisted of Au particles have been firstly prepared by a simple, fast, one-step method using o-phenylenediamine (o-PD) as a reducing agent at room temperature and characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. It has been demonstrated that the initial o-PD/Au molar ratio is a key factor to control the formation and size of single Au microballs through self-organization of Au particles using simultaneously formed o-PD oligomers with phenazyl-like structures as molecular linkers.     

Effects of TeOx films on temperature coefficients of delay of Love-type wave devices based on TeOx/36°YX-LiTaO3 structures

Tellurium oxide (TeO_x) thin films are prepared on 36°YX-LiTaO₃ substrates by RF magnetron sputtering technique under different deposition conditions. The structures and compositions of the TeO_x films are analyzed by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, which show that the TeO_x films are amorphous and with different ratios of Te to O prepared in different conditions. Then the Love-type wave devices based on TeO_x/36°YX-LiTaO₃ structures are fabricated, and the temperature coefficient of delay (TCD) of the Love-type wave devices are investigated. The results show that, when TeO_x films deposited at suitable deposition conditions, the TCD of the Love-type wave devices are less than that of the shear-horizontal (SH) wave devices fabricated on the bare 36°YX-LiTaO₃ substrates, which demonstrates that the TCD of the TeO_x films is negative. Moreover, the TCD of the devices are strongly dependent upon the preparation conditions and the thicknesses of the TeO_x films. Therefore, the TCD of the Love-type wave devices can be optimized by suitably selecting the preparation conditions and the thickness of TeO_x films.