CO2 laser assisted removal of UO2 and ThO2 particulates from metal surface

Pulsed laser assisted removal of uranium dioxide and thorium dioxide particulates from stainless steel surface have been studied using a TEA CO₂ laser. Decontamination efficiency is measured as a function of laser fluence and number of pulses. Threshold fluence for the removal of UO₂ particulates has been found to be lower than that required for the removal ThO₂ particulates. Usage of a ZnSe substrate, that is transparent to the laser wavelength used here, enabled us to decouple the cleaning effect arising out of absorption in the particulates from that in the substrate and has contributed towards understanding the mechanism responsible for cleaning. The experimental observations are also corroborated by simple theoretical calculations.     

Acoustic superscatterer and its multilayer realization

Picosecond (40 ps) pulsed Nd:YAG laser irradiation of a WTi thin film on silicon with a wavelength of 532 nm and a fluence 2.1 J/cm² was performed in air. This led to significant changes of the chemical composition and morphology on the surface of the WTi thin film. The results show an increase in surface roughness, due to formation of conical structures, about 50 nm wide in the base, and a very thin oxide layer composed of WO₃ and TiO₂, with a dominant TiO₂ phase at the top, within the depth of about 20 nm. The thickness of the oxide layer was dependent on the number of laser pulses. The samples were analyzed by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy.     

Adsorption of gold on oxidized tungsten

The kinetics of adsorption and desorption of gold atoms from the surface of a thin (<2 nm) oxide film grown on a textured W ribbon with the preferred emergence of the (100) face is studied using termal desorption spectrometry in a wide range of coatings. A single desorption phase is observed in the spectra of termal desorption of Au atoms from oxidized W. The activation energy of desorption of Au atoms from tungsten oxides is lower than the gold sublimation heat (it amounts to E = 3.1 eV for the concentration of adsorbate atoms on the surface corresponding to coverage θ _s = 2.38). The gold film on oxidized tungsten at room temperature grows in the form of 3D islands. The sticking coefficient for gold atoms at T = 300 K is close to unity in the coverage range 0.5 < θ _s < 2.5.     

Cathodoluminescence of thorium in the presence of O2, CO and gas mixtures of CO-O2 and CO-H2

The cathodoluminescence (2–6 keV incident electrons) observed from thorium (111) and (533) crystal faces was recorded and analyzed for surfaces produced under various conditions. The blue luminescence observed in the presence of a partial oxygen pressure ～ 133 μPa (～10^-6 Torr) was found to consist of a broad asymmetric major band that peaked around 468 nm on which weak bands or lines were superimposed at approximately 433, 489, 502, and 534 nm. The emission was almost totally extinguished in the presence of a partial CO pressure ～ 133 μPa (～10^-6 Torr). The thorium-oxygen cathodoluminescence (CL) is interpreted as arising from the formation of ThO₂ and the excitation of luminescence centers by the incident electron beam and their subsequent decay. The major luminescence at 468 nm arises from F centers in ThO₂. The weak bands at 433 and 534 nm may arise from surface F⁺ and F centers designated as F⁺_s and F_s. The former may also be due to an OH luminescence center. The two longer wavelength lines (489, 502 nm) superimposed on the broad major band at approximately 468 nm are interpreted as arising from Pr³⁺ impurities in the thorium lattice that gave rise to fluorescence emission. The line at 468 nm also may be due in part to the fluorescence of ThO. The cathodoluminescence spectra observed in the presence of CO, and (CO+O₂) and (CO+H₂) gas mixtures were consistent with an interpretation that O₂ in the gas phase was required in order to obtain ThO₂ on and below the surface to produce significant luminescence. Auger spectroscopy showed that exposure to CO left approximately as much oxygen on the surface as in the case of O₂ but did not produce appreciable cathodoluminescence.     

Laser-assisted decontamination—A wavelength dependent study

We present here the experimental results on cleaning of radioactive dielectric particulates, loosely deposited on stainless steel, by coherent light of 1064 nm wavelength and its three harmonics occurring at 532 nm, 355 nm and 266 nm, derived from an Nd-YAG laser. For the initial few exposures, the decontamination factor has been found to be highest when exposed to 1064 nm radiation. With increasing number of exposures, however, the radiation with reducing wavelength assumes a more important role as a cleaning agent. The observation of almost no cleaning with 1064 nm and much reduced cleaning with its harmonics when the contamination is deposited on a transparent substrate confirms the dominant role played by metal substrate towards expelling the loose particulates from its surface.     

Formation of combustible gases during interaction of tungsten and zirconium with supercritical fluid H2O/CO2

Oxidation of bulk samples of tungsten (923 K) and zirconium (773 and 873 K) by H₂O/CO₂ supercritical fluid (molar ratio [CO₂]/[H₂O] = 0.17–0.26) at a pressure of about 300 atm is investigated. Oxidation produces monoclinic WO₃, monoclinic W₁₉O₅₅, monoclinic ZrO₂, H₂, CO, CH₄, and carbon (on the surface of tungsten oxide). Differences in oxidation mechanisms for tungsten and zirconium are revealed. CO₂ molecules take part in the oxidation of tungsten only after oxide formation in reaction with H₂O. Zirconium is oxidized fully, and oxidation of tungsten terminates in the formation of the oxide layer at the metal surface.     

Radio-frequency assisted pulsed laser deposition of nanostructured WOx films

The synthesis of tungsten oxide films with large surface area is promising for gas sensing applications. Thin WO_x films were obtained by radio-frequency assisted pulsed laser deposition (RF-PLD). A tungsten target was ablated at 700 and 900 Pa in reactive oxygen, or in a 50% mixed oxygen-helium atmosphere at the same total pressure values. Corning glass was used as substrate, at temperatures including 673, 773 and 873 K. Other deposition parameters such as laser fluence (4.5 J cm⁻²), laser wavelength (355 nm), radiofrequency power (150 W), target to substrate distance (4 cm), laser spot area (0.7 mm²), and number of laser shots (12,000) were kept fixed. The sensitivity on the deposition conditions of morphology, nanostructure, bond coordination, and roughness of the obtained films were analyzed by scanning and transmission electron microscopy, micro-Raman spectroscopy, and atomic force microscopy.     

Pulsed laser deposition of TiO<Subscript>2</Subscript>: diagnostic of the plume and characterization of nanostructured deposits

Promising applications of TiO₂ nanostructures include the development of optical devices, sensors, photocatalysts and self-cleaning coatings. In view of their importance, research on the synthesis of nanosized TiO₂ is a particularly active field. In this work we report on the investigation of the effect of laser irradiation wavelength (Q-switched Nd:YAG laser at 532, 355 and 266 nm), the temperature of the substrate and the atmosphere of deposition (vacuum, Ar and O₂) that are suitable for obtaining nanostructured deposits from TiO₂ sintered targets. The ablation plume emission is characterized with spectral and temporal resolution by optical emission spectroscopy (OES), while the surface morphology and chemical states of the material deposited on a Si (100) substrate are examined by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM) and by X-ray photoelectron spectroscopy (XPS), respectively. Deposits with nanostructured morphology with grain size down to 40 nm and keeping the stoichiometry of the targets were obtained at high temperature, while the highest concentration of particulates was observed at the longest laser wavelength of 532 nm on a substrate heated up to 650°C. In situ characterization of the ablation plume, carried out by OES, indicated the presence of emissions assigned to Ti I, Ti II and O I.     

Formation of short-period multilayer W/B4C compositions

The quantitative characteristics of the interlayer interaction in multilayer W/B₄C periodic compositions produced by magnetron sputtering are studied by small-angle X-ray diffraction using CuK _?? radiation and by electron microscopy of transverse cuts. It is found that approximately 0.85 nm of the tungsten layer thickness is consumed for the formation of mixed zones at layer boundaries. The mixed layers have a density of 13.4 ± 0.7 g/cm³ and contain tungsten in a bound chemical state. The effect of these mixed zones on the X-ray reflectivity of multilayer W/B₄C compositions is estimated. A method is proposed to determine the layer thickness at a small number of peaks in an X-ray diffraction pattern.     

Determination of the reduction depth of tungsten oxide thin films under the effect of proton irradiation

This work is devoted to experimental determination of the limiting reduction depth of tungsten oxide to metal by the measurement of volumetric variations in a thin film of WO₃ under the effect of proton irradiation with an energy of 1.5 keV. The method of radiation-induced reduction of tungsten from WO₃ can be used for preparation of conducting structures in a dielectric matrix and obtaining an inorganic mask for carrying out different ion-beam processes. It is shown experimentally that the effect of a proton beam with an energy of 1.5 keV provides complete reduction of a tungsten oxide layer up to 138 nm thick. The experimental ratio of the thickness of the reduced layer to the thickness of the starting oxide film was 0.31. It is shown that the limiting reduction depth of tungsten oxide is determined by the path of protons in tungsten.     

Morphology and optical properties of p-type porous GaAs(1 0 0) layers made by electrochemical etching

Porous GaAs layers were formed by electrochemical etching of p-type GaAs(1 0 0) substrates in HF solution. A surface characterization has been performed on p-type GaAs samples using X-ray photoelectron spectroscopy (XPS) technique in order to get information about the chemical composition, particularly on the surface contamination. According to the XPS spectra, the oxide layer on as-received porous GaAs substrates contains As₂O₃, As₂O₅ and Ga₂O₃. Large amount of oxygen is present at the surface before the surface cleaning.Compared to untreated GaAs surface, room temperature photoluminescence (PL) investigations of the porous layers reveal the presence of two PL bands: a PL peak at ∼871 nm and a “visible” PL peak at ∼650-680 nm. Both peak wavelengths and intensities varied from sample to sample depending on the treatment that the samples have undergone. The short PL wavelength at 650-680 nm of the porous layers is attributed to quantum confinement effects in GaAs nano-crystallites. The surface morphology of porous GaAs has been studied using atomic force microscopy (AFM). Nano-sized crystallites were observed on the porous GaAs surface. An estimation of the mean size of the GaAs nano-crystals obtained from effective mass theory and based on PL data was close to the lowest value obtained from the AFM results.     

The lithiation studies of nanostructured tungsten oxide film prepared via electrochemical precipitation

In this work, nanostructured tungsten oxide was electrodeposited by cyclic voltammetric technique onto a stainless steel surface. The structure and surface morphology of the resulting oxide film were characterized by means of X-ray diffraction, scanning probe microscopy, and scanning electron microscopy. The electrochemical intercalation of lithium into the nanostructured tungsten oxide was studied using cyclic voltammetry, galvanostatic charge–discharge curves, and electrochemical impedance spectroscopy in a liquid electrolyte consisting of 1 M LiClO₄ in propylene carbonate. The as-deposited tungsten oxide indicated the capacity for electrochemical lithium insertion. The specific capacitance of 108.05 F?g^?1 was obtained at the constant discharge density of 0.07 mA?cm^?2.     

Changes of structure and composition of a zinc ion-implanted silicon surface during nanoparticle formation upon thermal treatment

Data from investigating the formation of nanoparticles (NPs) on a surface of silicon wafers after zinc ion implantation and thermal annealing are presented. The investigation is conducted by means of trans-mission electron microscopy, electron diffraction analysis, energy dispersive microanalysis, scanning tunneling microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. It is found that on their surfaces, the implanted samples have only films of amorphous silicon containing implanted zinc, oxygen, and carbon contamination. Thermal treatment in the range of 400–800°C leads to the formation NP with 20–50 nm wide and 10 nm tall on a wafer’s surface, plus a silicon oxide layer about 20 nm thick. NPs are composed of zinc compounds of the ZnO, ZnSiO₃, or Zn₂SiO₄ types. These NPs disappear after annealing at 1000°C.     

Gold nano-wires and nano-layers at laser-induced nano-ripples on PET

Gold nano-layers were deposited onto laser irradiated polyethyleneterephthalate (PET) surfaces. For irradiation, we used the linearly polarized light of a pulsed 248 nm KrF and 157 nm F₂ laser, respectively. In a certain range of irradiation parameters, the irradiation resulted in the formation of coherent ripples patterns with a lateral periodicity in the order of the wavelength of the laser light and with a corrugation height of several 10 nm. The deposited layers were then prepared by sputtering. The layers were analyzed by atomic force microscopy (AFM), focused ion beam (FIB) cuts, scanning electron microscopy (SEM), and angular resolved X-ray induced photoelectron spectroscopy (ARXPS). Gold sputtering on KrF laser irradiated PET led to the formation of separated “nano-wires” at the ridges of the nano-patterns and not to a continuous metal layer, as we obtained in case of gold sputtering onto F₂ irradiated PET. The results of the XPS analysis indicated, that the KrF irradiation caused degradation on the ridge of the ripples, whereas no noticeable degradation occurred for F₂ laser treatment. We attribute the different growth mechanisms of the deposited gold layers mainly to the difference in surface chemical composition of laser irradiated PET with the two different lasers employed.     

Nd:YAG laser synthesis of nanostructural V2O5 from vanadium oxide sols: Morphological and structural characterizations

Vanadium oxide thin films were prepared by sol-gel method, then subjected to Nd:YAG laser (CW, 1064 nm) radiation. The characteristics of the films were changed by varying the intensity of the laser radiation. The nanocrystalline films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). XRD revealed that above 102 W/cm² the original xerogel structure disappears and above 129 W/cm² the films become totally polycrystalline with an orthorhombic structure. From TEM observations, we can see that due to laser radiation, the originally fibrillar-like particles disappear and irregular shaped, layer structured V₂O₅ particles are created. From XPS spectra we can conclude that due to laser radiation the O/V ratio increased with higher intensities.     

Laser type of spectral narrowing in electroluminescent Si/SiO2superlattices prepared by low-pressure chemical vapour deposition

Si/ SiO₂superlattices were fabricated by low-pressure chemical vapour deposition. Superlattices of 75–150 nm layer pair thicknesses and having 1–8 layer pairs were investigated in order to evaluate their surface structure and electroluminescent properties. Atomic force microscopy (AFM) studies were performed in order to investigate the surface morphology of a thin SiO₂layer and to evaluate the sizes of polysilicon nanocrystals grown onto the top of it. The current–voltage characteristics and the electroluminescence spectra are also shown. We have observed a blueshift of over 200 nm in the electroluminescence peak wavelength by increasing the driving current. The change in the direction of the driving current through a sample changes the peak wavelength from the yellow to red region. In some samples, we could detect an exponential increase in light intensity in current densities near 100 mA per square millimeter. The increase in intensity is combined with a very prominent spectral narrowing of the electroluminescence spectra. The half width of this spectral peak was less than 5 nm. It is possible that we have observed for the first time a laser type of mechanism in semiconductor structures made solely of silicon and silicon dioxide.     

Microstructuring of Si(100) by light induced dry etching in the VUV

Light-induced dry etching of Si(100) in the VUV range using synchrotron radiation (SR) and a halogen-containing gas (XeF₂) has been investigated with respect to selectivity, anisotropy, quantum efficiency, optimal wavelength, spatial resolution and quality of the photochemical etching processes. Microstructuring of Si with XeF₂can be optimized to achieve etched structures in the sub-micrometre range by increasing the contrast in choosing a wavelength with minimal unselective etching. The strength of unselective etching is strongly wavelength dependent and follows the XeF₂gas phase absorption coefficient. Fragments from dissociation of the XeF₂reach the Si surface and thus cause unselective etching. Optimal dry etching occurs for wavelengths around 120 nm because the selectivity is high due to an excitation of a surface layer and also the quantum efficiency is very large. An efficiency of 10 removed Si atoms per incoming photon, which exceeds that in the visible spectral range by more than four orders of magnitude, combined with the higher spatial resolution at 120 nm compared to the conventional excimer laser and I-line wavelengths and the availability of optical materials for imaging present a perspective for generating line densities in the Gbit range.     

Structure and electrical properties of tungsten oxide nanorods epitaxially organized on a mica substrate

Our objective was to fabricate nanosized tungsten oxide rods and to test their sensing properties. In the present report, we focus on the crystallographical structure and the electrical properties of tungsten nanorods. The tungsten oxide nanorods were grown by vapor transport from a WO₃ layer onto a substrate (Mica). The nanorods growth was controlled by the temperature gradient between the WO₃ layer and the substrate. Their morphology was investigated by AFM and their structure by TED and TEM. We have investigated the conductivity of the WO₃ nanorods with a technique derived from atomic force microscopy operating in contact mode with a conductive tip (C-AFM). Its provides at the same time a classical topographic image of the sample surface and an image representative of the local electrical resistance between the tip and a metallic contact on the substrate. We also investigated the electrical properties of the WO₃ nanorods by the current-voltage responses in a bias range of 0 ± 1 V. We have performed experiments in an environmental chamber and characterized the role of water vapor on the electrical conductivity of WO₃ nanorods.     

Transient-enhanced Si diffusion on natural-oxide-covered Si(0 0 1) nano-structures during vacuum annealing

The morphology of annealed patterned Si(0 0 1) wire templates was studied by several techniques. We found an enormous Si-mass transport on the Si surface at usual oxide desorption temperatures around 900°C under UHV conditions. Heat treatment of 5 min transforms the initially rectangular wire profiles with a height of 300 nm to flat (<100 nm) and faceted triangular ridges exhibiting thermodynamically preferred {1 1 1}- and {3 1 1}-facets.It was found that the natural SiO₂ on the predefined wire pattern must be responsible for the degradation of the wire structure. Removing the SiO₂ layer from the Si wires ex situ with an HF dip preserves the rectangular structures during high-temperature annealing. The Si–SiO₂ interface was investigated with high-resolution transmission electron microscopy to image the Si wire surface and the natural oxide layer in detail.