A high-sensitivity laser microprobe mass analyzer

A laser microprobe mass analyzer has been developed. It is intended for application in biomedical and physiological research. A frequency-doubled ruby laser is focussed through an incident light microscope to a spot of minimally 0.5 μm in diameter on a thin section specimen of 0.1–1.5 μm thickness. The microplasma generated from the irradiated volume is analyzed in a time-of-flight mass spectrometer recording the complete spectrum for each shot. From lithium doped epoxy resin (5 ppm by weight), used as an organic standard, 1.4×10⁻¹⁹g or 1.4×10⁴ atoms of the⁶Li isotope have been detected. This sensitivity corresponds to that of ion microprobes but is at least an order of magnitude higher than obtained with electron probe X-ray microanalyzers.     

Structural phase changes in a titanium-silicon system modified by high-current electron beams and compression plasma flows

Structural phase changes in a titanium-silicon system treated by low-energy high-current electron beams (HCEBs) and compression plasma flows (CPFs) with the duration 100 μs and the energy density 12–15 J/cm² are studied. Scanning electron microscopy, X-ray diffraction and electron microprobe analysis are used in this work. The formation of a titanium-doped silicon layer 10–25 μm thick, titanium silicides (TiSi₂ under HCEBs and Ti₅Si₃ under CPF treatment), silicon dendrites, and needle-like eutectics (typical size of precipitates is about 50 nm) is revealed. It is shown via the results of numerical simulation that the thickness of the metal-doped layer is mainly controlled by the power density value and the surface nonuniformity of the heat flow over the target surface. The thermodynamic regularities of phase formation are discussed, taking into account heat transfer between the silicide nuclei and solid silicon.     

Structure and phase composition of a chromium-silicon system modified by high-current electron beams

The results of studies of the structure-phase state of a chromium-coated silicon substrate system’s subsurface layer treated with low-energy high-current electron beams, 50–200 μs in duration and with an energy density of 15 J/cm², are reported. The data of raster electron microscopy and X-ray structural and spectral microanalysis revealed the formation of a chromium-doped silicon layer with a thickness of 2–38 μm, chromium-enriched silicon dendrites, chromium disilicide CrSi₂, and an amorphous eutectic layer (the characteristic cross-section size of the chromium-enriched phase extrusions is ∼50 nm). The structure-phase transformations are discussed taking into account the peculiarities of the distribution of temperature, diffusion and convective mass-transfer in the modified layer.     

Electron microscopy investigation of AlMg6 aluminum alloy surface defects caused by microorganisms extracted in space stations

The surfaces of AMg6 (aluminum-magnesium) alloy samples that have passed accelerated biocorrosion tests have been investigated in a Quanta-3D scanning electron microscope. The alloy samples have been treated with the Ulocladium botrytis Preuss fungus, which is an active destructive fungus and was previously extracted on surfaces of the International Space Station. Biocorrosion pits 2–10 μm in diameter, cavities the depths of which can reach 70–250 μm depth, and spots of modified color are found to be the most typical defects. The surfaces of large cavities consist of faceted cubic particles that are formed when the acid products of fungus metabolism interact with the alloy surface. The particles have an average size of 30 μm, which is close to the size of alloy grains. The microstructure of a biocorrosion layer has been investigated in a Quanta-3D microscope with the use of a focused Ga⁺ ion beam. The samples of 12-μm-wide transverse slices are obtained near large cavities and investigated in a Tecnai G₂₃0ST transmission electron microscope. The X-ray microanalysis of the defective layer has revealed the high concentration of oxygen in this layer. Obtained images indicate that the corrosion cavity surface has a complex porous structure.     

The influence of low-intensity beta radiation on crack susceptibility under indentation of silicon

The dependence of the lengths of radial cracks formed during indentation of silicon single crystals on the depth of imprint has been studied using electron microscopy. The influence of low-intensity (I = 10⁵ cm⁻² s^–1) beta radiation on the crack susceptibility during indenter penetration to a depth of ∼2.5 μm has been revealed.     

Gold nanoparticle induced conformational changes in heme protein

Change of α-helical structure of heme protein (Hb) to a β-sheet and random coil conformation because of the interaction of glycine capped gold nanoparticles (20–60 nm) as observed from attenuation total reflectance, absorption, Fourier transform infra red, and Circular Dichroism spectroscopy has been reported in this article. Upon interaction, protein takes a cylindrical shape of length 12 μm and diameter 0.35 μm as revealed from scanning electron microscopy and transmission electron microscopy. The Selected-Area Electron beam Diffraction pattern shows change of crystalline structure in GNP to amorphous nature with the interaction of Hb.     

Direct patterning of gold oxide thin films by focused ion-beam irradiation

For direct writing of electrically conducting connections and areas into insulating gold oxide thin films a scanning Ar⁺ laser beam and a 30 keV Ga⁺ focused ion beam (FIB) have been used. The gold oxide films are prepared by magnetron sputtering under argon/oxygen plasma. The patterning of larger areas (dimension 10–100 μm) has been carried out with the laser beam by local heating of the selected area above the decomposition temperature of AuO_x (130–150 °C). For smaller dimensions (100 nm to 10 μm) the FIB irradiation could be used. With both complementary methods a reduction of the sheet resistance by 6–7 orders of magnitude has been achieved in the irradiated regions (e.g. with FIB irradiation from 1.5×10⁷ Ω/□ to approximately 6 Ω/□). The energy-dispersive X-ray analysis (EDX) show a considerably reduced oxygen content in the irradiated areas, and scanning electron microscopy (SEM), as well as atomic force microscopy (AFM) investigations, indicate that the FIB patterning in the low-dose region (10¹⁴ Ga⁺/cm²) is combined with a volume reduction, which is caused by oxygen escape rather than by sputtering. Received: 30 May 2000 / Accepted: 31 May 2000 / Published online: 13 July 2000     

Pulsed electron-beam melting of a copper — steel 316 system: Evolution of the chemical composition,microstructure, and properties

The surface topography, chemical composition, microstructure, nanohardness, and tribological characteristics of a Cu (film, 512 nm)-stainless steel 316 (substrate) system subjected to pulsed melting by a low-energy (20–30 keV), high-current electron beam (2–3 μs, 2–10 J/cm²) were investigated. The film was deposited by sputtering a Cu target in the plasma of a microwave discharge in argon. To prevent local exfoliation of the film due to cratering, the substrate was multiply pre-irradiated with 8–10 J/cm². On single irradiation, the bulk of the film survived, and a diffusion layer containing the film and substrate components was formed at the interface. The thickness of this layer was 120–170 nm irrespective of the energy density. The diffusion layer consisted of subgrains of γ-Fe solid solution and nanosized particles of copper. In the surface layer of thickness 0.5–1 μm, which included the copper film quenched from melt and the diffusion layer, the nanohardness and the wear resistance nonmonotonicly varied with energy density, reaching, respectively, a maximum and a minimum in the range 4.3–6.3 J/cm². As the number of pulsed melting cycles was increased to five in the same energy density range, there occurred mixing of the film-substrate system and a surface layer of thickness ∼2 μm was formed which contained ∼20 at. % copper. Displacement of the excess copper during crystallization resulted in the formation of two-phase nanocrystal interlayers separating the γ-phase grains. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 6–13, December, 2005.     

Surface relief and structure of electroexplosive composite surface layers of the molybdenum-copper system

The surface topography and structure of copper layers exposed to multiphase plasma jets of products of electrical explosion of molybdenum and copper foils are studied using profilometry and scanning electron and light microscopy. Such treatment allows deposition of either layered coatings or alloyed composite layers. It is found that the surface layer roughness parameter is R _a = 3.2−4.0 μm. The thickness of some copper and molybdenum layers of coatings is 15–20 μm. Electroexplosive alloying produces layers 25 μm thick. Sizes of copper inclusions in the molybdenum matrix near the surface of such layers vary from 30 nm to 1–2 μm.     

Fabrication of two types of one-dimensional Si–C nanostructures by laser ablation

Two types of one-dimensional (1D) nanostructures—amorphous silicon carbide (SiC) nanowires, 5–30 nm thick and 0.5–2 μm long, and carbon nanotubes (CNTs) filled completely with crystalline SiC nanowires, 10–60 nm thick and 2–20 μm long—were synthesized by the laser ablation of carbon-silicon targets in the presence of high-pressure Ar gas up to 0.9 MPa. All the CNTs checked by transmission electron microscopy contained SiC, and no unfilled CNTs were produced. We discuss the growth of the two nanostructures based on the formation of molten Si–C composite particles and their instabilities leading to the precipitation of Si and C.     

Synthesis of Yb-doped Ba(Ce,Zr)O3 ceramic powders by sol–gel method

This study was aimed to synthesize a ceramic electrolyte of BaCe_0.76Zr_0.19Yb_0.05O_2.975 using acetate and chloride precursors. The transparent sol was stable for more than 10 months but only 3 months for the gel. The dried gel was characterized using thermogravimetric analysis/differential scanning calorimetry, particle analyzer, X-ray diffraction (XRD), and scanning electron microscopy/dispersive X-ray (SEM/EDX) analysis. Thermal behavior analysis showed three steps of weight losses. All the processes were exothermic reactions as shown by derivative thermogravimetric analysis signal. Two groups of particle size were observed in the particle size distribution for the sample in the form of sol and powders ranging from 100 to 1,100 nm. A high purity single-phase sample with orthorhombic structure was identified by XRD. The theoretical density estimated from the unit cell parameters was 6.40 g cm⁻³. SEM of the powdered sample showed homogeneous distribution of particles and the grains size were in the range of 0.7–1.3 μm. EDX data revealed that the residue of small amount of chloride (≈0.25%) was still present in the final product of the compound.     

Structure,transport and field-emission properties of compound nanotubes: CN<Subscript>x</Subscript> vs. BNC<Subscript>x</Subscript> (<Emphasis Type="Italic">x</Emphasis><0.1)

Transport and field-emission properties of as-synthesized CN_x and BNC_x (x<0.1) multi-walled nanotubes were compared in detail. Individual ropes made of these nanotubes and macrofilms of those were tested. Before measurements, the nanotubes were thoroughly characterized using high-resolution and energy-filtered electron microscopy, electron diffraction and electron-energy-loss spectroscopy. Individual ropes composed of dozens of CN_x nanotubes displayed well-defined metallic behavior and low resistivities of ∼10–100 kΩ or less at room temperature, whereas those made of BNC_x nanotubes exhibited semiconducting properties and high resistivities of ∼50–300 MΩ. Both types of ropes revealed good field-emission properties with emitting currents per rope reaching ∼4 μA(CN_x) and ∼2 μA (BNC_x), albeit the latter ropes se- verely deteriorated during the field emission. Macrofilms made of randomly oriented CN_x or BNC_x nanotubes displayed low and similar turn-on fields of ∼2–3 V/μm. 3 mA/cm² (BNC_x) and 5.5 mA/cm² (CN_x) current densities were reached at 5.5 V/μm macroscopic fields. At a current density of 0.2–0.4 mA/cm² both types of compound nanotubes exhibited equally good emission stability over tens of minutes; by contrast, on increasing the current density to 0.2–0.4 A/cm², only CN_x films continued to emit steadily, while the field emission from BNC_x nanotube films was prone to fast degradation within several tens of seconds, likely due to arcing and/or resistive heating. Received: 29 October 2002 / Accepted: 1 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Synthesis of C–N nanotube blocks and Y-junctions in bamboo-like C–N nanotubes

We report the observations made on the synthesis and characterization of C–N nanotube blocks and Y-junctions in bamboo-like C–N nanotubes. The C–N nanotube Blocks have been synthesized by pyrolyzing the mixture of silver nitrate acetonitrile solution and ferrocene benzene solution. The structural/microstructural characterization of the as-synthesized material has been done using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopic (XPS) analysis has been carried out to confirm the presence of nitrogen in nanotubes. These investigations reveal the formation of blocks of bamboo-like nanotubes having the dimension 300 × 200 × 30 μm and the diameter is 20–50 nm. We also observe the formation of Y-junctions in bamboo-like nanotubes as we spray the acetonitrile ferrocene and AgNO₃ mixture. The length of the synthesized Y-junction nanotube bundles is ~2 μm. Some more complex Ψ-shaped junctions are also found to be present. The diameters of the Y-junction nanotubes is ~80 nm at the junction and 25–50 nm at the branches.     

Synthesis of High Quality CdS Nanorods by Solvothermal Process and their Photoluminescence

Large-scale cadmium sulfide (CdS) nanorods with high quality were successfully synthesized by solvothermal method using ethylenediamine (en) aqueous as solvent. The as-obtained product was investigated by X-ray diffractometer (XRD), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FE-SEM), ultraviolet–visible (UV–Vis) spectrum and photoluminescence (PL) spectrum. The length and width of the CdS nanorods were in the range of 1–2 μm, 30–40 nm, respectively. XRD analysis revealed that the crystal structure of the product was hexagonal phase. Photoluminescence measurement showed that the nanobelts have two main emission bands around 470 and 560 nm, which should come from the higher-level transition and the intrinsic transition, respectively.     

Phase transformation during surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser

Surface ablation of cobalt-cemented tungsten carbide hard metal has been carried out in this work using a 308 nm, 20 ns XeCl excimer laser. Surface microphotography and XRD, as well as an electron probe have been used to investigate the transformation of phase and microstructure as a function of the pulse-number of laser shots at a laser fluence of 2.5 J/cm². The experimental results show that the microstructure of cemented tungsten carbide is transformed from the original polygonal grains of size 3 μm to interlaced large, long grains with an increase in the number of laser shots up to 300, and finally to gross grains of size 10 μm with clear grain boundaries after 700 shots of laser irradiation. The crystalline structure of the irradiated area is partly transformed from the original WC to βWC_1-x, then to αW₂C and CW₃, and finally to W crystal. It is suggested that the undulating ‘hill–valley’ morphology may be the result of selective removal of cobalt binder from the surface layer of the hard metal. The formation of non-stoichiometric tungsten carbide may result from the escape of elemental carbon due to accumulated heating of the surface by pulsed laser irradiation. Received: 13 July 2000 / Accepted: 27 October 2000 / Published online: 10 January 2001     

EPR Investigation of Radical-Production Cross Sections for Sucrose and L-alanine Irradiated with X-rays and Heavy-ions

Using electron paramagnetic resonance (EPR), we investigated stable radical-production cross sections (σ) of sucrose and L-alanine radicals produced by heavy-ion irradiations with various linear energy transfers (LET). The heavy-ion irradiation results were compared with those of X-ray irradiation at the same dose. The EPR signal areas for the two compounds showed a linear relation with the absorbed dose, as well as a logarithmic correlation with the LET. Further analysis was carried out for the radical-production cross section, which showed that stable radicals of the two compounds were produced through collisions of several particles with a single molecule. The relative σ value of sucrose for C ion irradiation was (1.29 ± 0.64) × 10⁻¹² μm². The σ value of alanine for C ion irradiation was (6.83 ± 0.42) × 10⁻¹³ μm². Considering the structural molecular sizes of sucrose and alanine, the σ values are similar. In addition, a comparison of the EPR results for the C ions and X-rays at 50 Gy dose was made. Sucrose spin concentrations produced by C ions at the LET value of 13.1 keV/μm and X-rays were similar unlike alanine. Thus, the noble EPR results with X-ray and heavy-ion irradiations imply that sucrose can be useful as a radiation indicator.     

Micro-hole fabricated inside FOTURAN glass using femtosecond laser writing and chemical etching

Vertical micro-holes were fabricated inside a photosensitive glass (FOTURAN) by focused femtosecond laser (λ = 775 nm) writing, followed by heat treatment and wet chemical etching in 8% hydrofluoric acid solution for 50 min. The micro-holes were analyzed by optical and scanning electron microscopy, and was found they own circular cross-section and clear edge. At present, micro-holes with aspect ratio of about 7 is achieved. By varying the incident laser fluence in a range of 2.3–36.2 J/cm² and the laser writing velocity in 100–1000 μm/s, the influences of femtosecond laser parameters on the formation of micro-holes are characterized as that: writing velocities hardly affect the micro-hole diameter, while relatively lower laser fluences result in smaller diameter, and the cross-section is more circular in this case. The possible reason for this phenomenon is discussed.     

Indium tin oxide nanowires growth by dc sputtering

Indium tin oxide nanowires have been grown by dc sputtering on different substrates without the use of catalysts or oblique deposition. The nanowire length was of the order of several μm, while their diameter was ∼50–100 nm. Small side branches on the nanowires were frequently observed. The nanowires were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The growth mechanism of the nanowires is discussed.     

Paramagnetic properties of single-crystal silicon implanted with iron-group transition metals

Samples of single-crystal silicon implanted with iron-group ions are investigated by electron paramagnetic resonance (EPR). The change in relative permittivity μ_r of the silicon layer modified by implanted nickel ions is found. The accumulation kinetics of paramagnetic centers of amorphous regions of silicon implanted with Co, Ni, and Fe are shown to be different. Magnetic hysteresis for both the wide EPR line due to implanted impurities and the EPR line due to dangling chemical silicon bonds is found. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 197–201, March–April, 2008.