Formation of partially embedded Au nanostructures: Ion beam irradiation on thin film.

The Au partially embedded nanostructure (PEN) is synthesized by ion irradiation on an Au thin film deposited on a glass substrate using a 50 keV Ar ion. Scanning electron microscopy results show ion beam-induced restructuring from irregularly shaped nanostructures (NSs) to spherical Au NSs, and further ion irradiation leads to the formation of well-separated spherical nanoparticles. Higuchi's algorithm of surface analysis is utilized to find the evolution of surface morphology with ion irradiation in terms of the Hurst exponent and fractal dimension. The Au PEN is evidenced by Rutherford backscattering spectrometry and optical studies. Also, the depth of the mechanism behind synthesized PEN is explained on the basis of theoretical simulations, namely, a unified thermal spike and a Monte Carlo simulation consisting of dynamic compositional changes (TRIDYN). Another set of plasmonic NSs was formed on the surface by thermal annealing of the Au film on the substrate. Glucose sensing has been studied on the two types of plasmonic layers: nanoparticles on the surface and PEN. The results reveal the sensing responses of both types of plasmonic layers. However, PEN retains its plasmonic behavior as the NSs are still present after washing with water, which demonstrates the potential for reusability. RESEARCH HIGHLIGHTS: Synthesis of PENs by ion irradiation Utilization of Higuchi's algorithm to explore the surface morphology. Unified thermal spike and TRIDYN simulations being used to explain the results. Glucose is only used as a test case for reusability of substrate.

Investigating ripple pattern formation and damage profiles in Si and Ge induced by 100 keV Ar+ ion beam: a comparative study.

Desired modifications of surfaces at the nanoscale may be achieved using energetic ion beams. In the present work, a complete study of self-assembled ripple pattern fabrication on Si and Ge by 100 keV Ar+ ion beam bombardment is discussed. The irradiation was performed in the ion fluence range of ≈3 × 1017 to 9 × 1017 ions/cm2 and at an incident angle of θ ≈ 60° with respect to the surface normal. The investigation focuses on topographical studies of pattern formation using atomic force microscopy, and induced damage profiles inside Si and Ge by Rutherford backscattering spectrometry and transmission electron microscopy. The ripple wavelength was found to scale with ion fluence, and energetic ions created more defects inside Si as compared to that of Ge. Although earlier reports suggested that Ge is resistant to structural changes upon Ar+ ion irradiation, in the present case, a ripple pattern is observed on both Si and Ge. The irradiated Si and Ge targets clearly show visible damage peaks between channel numbers (1000-1100) for Si and (1500-1600) for Ge. The clustering of defects leads to a subsequent increase of the damage peak in irradiated samples (for an ion fluence of ≈9 × 1017 ions/cm2) compared to that in unirradiated samples.

Fabrication of thin Molybdenum backed target using rolling method.

A successful attempt was made to fabricate a thin foil of natural Mo target on a thick Au backing with Indium in between to improve adhesion between the foils. Rolling at elevated temperature was considered to fabricate Mo foil while gold foil was fabricated employing conventional rolling technique. The heating of Mo foil under natural environment lead to the oxidation or carbonization on foil surface which was confirmed through Energy Dispersive X-ray Spectroscopy (EDS) measurements. Indium of thickness ∼86µg/cm2 was evaporated on Mo foil to improve adhesion between Mo and Au foils. The characterization of fabricated thin Mo foil was done using the Energy Dispersive X-ray Spectroscopy (EDS) and the Scanning Electron microscope (SEM) techniques. Thickness measurement of the target (Mo-Au) was done using Energy Dispersive X-ray Fluorescence (EDXRF) technique, in the measurements the thickness of the Mo foil and of gold backing are found out to be 1.3 mg/cm2 and 9 mg/cm2 respectively.

A Thrifty Liquid-Phase Exfoliation (LPE) of MoSe2 and WSe2 Nanosheets as Channel Materials for FET Application.

Two-dimensional materials are trending nowadays because of their atomic thickness, layer-dependent properties, and their fascinating application in the semiconducting industry. In this work, we have synthesized MoSe2 and WSe2 nanosheets (NSs) via a liquid-phase exfoliation method and investigated these NSs as channel materials in field-effect transistors (FET). The x-ray diffraction (XRD) pattern revealed that the synthesized NSs have a 2H phase with 0.65 nm d-spacing which belongs to the (002) Miller plane. Transmission electron microscopy (TEM) studies revealed that MoSe2 and WSe2 have a nanosheet-like structure, and the average lateral dimensions of these NSs are ~ 25 nm and ~ 63 nm, respectively. From Raman spectra, we found that the intensity of the A1g vibrational mode decreases with the reduction in the number of layers. UV-visible spectroscopy revealed that the bandgap values of MoSe2 and WSe2 NSs are 1.55 eV and 1.50 eV, respectively, calculated using the Tauc equation. The output and transfer characteristics of the FET devices reveals that the fabricated FETs have good ohmic contact with the channel material and an ON/OFF current ratio of about 102 for both devices. This approach for the fabrication of FET devices can be achieved even without sophisticated fabrication facilities, and they can be applied as gas sensors and phototransistors, among other applications.

Spatial distribution of fossil fuel derived CO2 over India using radiocarbon measurements in crop plants.

Examining the contribution of fossil fuel CO2 to the total CO2 changes in the atmosphere is of primary concern due to its alarming levels of fossil fuel emissions over the globe, specifically developing countries. Atmospheric radiocarbon represents an important observational constraint and utilized to trace fossil fuel derived CO2 (CO2ff) in the atmosphere. For the first time, we have presented a detailed analysis on the spatial distribution of fossil fuel derived CO2 (CO2ff) over India using radiocarbon (Δ14C) measurements during three-year period. Analysis shows that the Δ14C values are varying between 29.33‰ to -34.06‰ across India in the year 2017, where highest value belongs to a location from Gujarat while lowest value belongs to a location from Chhattisgarh. Based on the Δ14C patterns, spatial distributions of CO2ff mole fractions have been determined over India and the calculated values of CO2ff mole fractions are varying between 4.85 ppm to 26.59 ppm across India. It is also noticed that the highest CO2ff mole fraction is observed as 26.59 ppm from a site in Chhattisgarh. CO2ff mole fraction values from four high altitude sites are found to be varied between 4.85 ppm to 14.87 ppm. Effect of sampling different crop plants from the same growing season and different crop plant organs (grains, leaves, stems) on the Δ14C and CO2ff have been studied. Annual and intra seasonal variations in the Δ14C and CO2ff mole fractions have also been analyzed from a rural location (Dholpur, Rajasthan).

Sustainable Bioengineering of Gold Structured Wide-Area Supported Catalysts for Hand-Recyclable Ultra-Efficient Heterogeneous Catalysis.

Metal nanoparticles grafted within inert and porous wide-area supports are emerging as recyclable, sustainable catalysts for modern industry applications. Here, we bioengineered gold nanoparticle-based supported catalysts by utilizing the innate metal binding and reductive potential of eggshell as a sustainable strategy. Variable hand-recyclable wide-area three-dimensional catalysts between ∼80 ± 7 and 0.5 ± 0.1 cm2 are generated simply by controlling the size of the support. The catalyst possessed high-temperature stability (300 °C) and compatibility toward polar and nonpolar solvents, electrolytes, acids, and bases facilitating ultra-efficient catalysis of accordingly suspended substrates. Validation was done by large-volume (2.8 liters) dye detoxification, gram-scale hydrogenation of nitroarene, and the synthesis of propargylamine. Moreover, persistent recyclability, monitoring of reaction kinetics, and product intermediates are possible due to physical retrievability and interchangeability of the catalyst. Finally, the bionature of the support permits ∼76.9 ± 8% recovery of noble gold simply by immersing in a royal solution. Our naturally created, low-cost, scalable, hand-recyclable, and resilient supported mega-catalyst dwarfs most challenges for large-scale metal-based heterogeneous catalysis.

Domain state modulation by interfacial diffusion in FePt/FeCo thin films: experimental approach with micromagnetic modelling.

We report the complex implications of inter-diffusion between polycrystalline FePt/FeCo layers as an impact of the FeCo underlayer on the structural and magnetic properties of the system. The crystalline growth of FePt strongly reduces in an entirely diffused system compared to the one with lesser diffusion, while the crystalline structure of FeCo is apparently less affected. Charge redistribution occurs between Fe, Co and Pt ensuring increased Co-Pt and Fe-Pt interactions with higher diffusion. Thereafter, we combine hysteresis and magnetic force microscopy measurements to show that the interfacial deformations result in the distinct out-plane magnetic behaviour of the system. FeCo@FePt nano-composite like structure, originating due to interfacial diffusion, shows interactions between two magnetic phases with in-plane low anisotropy exhibiting wasp-shaped out-plane hysteresis loop. Whereas the layered structure of FePt/FeCo films shows random anisotropy with a significant out-plane contribution even in the polycrystalline films. Micromagnetic modelling demonstrates coercivity deterioration and reduction of switching field due to the formation of a slightly diffused interface. Contrarily, the experimental observations for complete diffusion between the two layers are explained by simulating the inhomogeneous distribution of anisotropies along the film plane. These studies provide deep perceptions of the magnetic properties of FePt/FeCo system governed by diffusion kinetics which are valuable to achieve desired magnetic characteristics using this system.

Reversible hydrogen control of antiferromagnetic anisotropy in α-Fe2O3.

Antiferromagnetic insulators are a ubiquitous class of magnetic materials, holding the promise of low-dissipation spin-based computing devices that can display ultra-fast switching and are robust against stray fields. However, their imperviousness to magnetic fields also makes them difficult to control in a reversible and scalable manner. Here we demonstrate a novel proof-of-principle ionic approach to control the spin reorientation (Morin) transition reversibly in the common antiferromagnetic insulator α-Fe2O3 (haematite) - now an emerging spintronic material that hosts topological antiferromagnetic spin-textures and long magnon-diffusion lengths. We use a low-temperature catalytic-spillover process involving the post-growth incorporation or removal of hydrogen from α-Fe2O3 thin films. Hydrogenation drives pronounced changes in its magnetic anisotropy, Néel vector orientation and canted magnetism via electron injection and local distortions. We explain these effects with a detailed magnetic anisotropy model and first-principles calculations. Tailoring our work for future applications, we demonstrate reversible control of the room-temperature spin-state by doping/expelling hydrogen in Rh-substituted α-Fe2O3.

Nano-scale depth-varying recrystallization of oblique Ar+ sputtered Si(111) layers.

Silicon, the workhorse of semiconductor industry, is being exploited for various functional applications in numerous fields of nanotechnology. In this paper, we report the fabrication of depth controllable amorphous silicon (a-Si) layers under 80 keV Ar+ ion sputtering at off-normal ion incidences of 30°, 40° and 50° and crystallization of these amorphous Si(111) layers under thermal annealing. We find that the irradiated samples were not fully amorphized even for the lowest oblique incidence of 30°. Sputtering at off-normal incidences induces depth controllable surface amorphization in Si(111). Annealing at temperature of 1,073 K is characterized by formation of depth-varying buried amorphous layer due to defect recrystallization and damage recovery. Some remnant tensile stress has been observed for recrystallized samples even for lowest oblique incidence. The correlation of amorphization and stress due to sputtering induced by oblique incidence has been discussed systematically. The possible mechanism of recrystallization is discussed in terms of vacancies produced in sputtering dominated regime and their migration during annealing treatment. Our results reveal that with appropriate selection of oblique ion beam sputtering parameters, depth controllable surface amorphization and recrystallization may be fine-tuned to achieve co-existing amorphous and crystalline phases, playing a crucial role in fabrication of substrates for IC industry.

Oxygen vacancy mediated cubic phase stabilization at room temperature in pure nano-crystalline zirconia films: a combined experimental and first-principles based investigation.

We report here the stabilization of the cubic phase under ambient conditions in the thin films of zirconia synthesized by electron beam evaporation. The cubic phase stabilization was achieved without the use of chemical stabilizers and/or concurrent ion beam bombardment. Films of two different thicknesses (660 nm and 140 nm) were deposited. While the 660 nm as-deposited films were in the cubic phase, as indicated by X-ray diffraction and Raman spectroscopy, the 140 nm as-deposited films were amorphous and the transformation to the cubic phase was obtained after thermal annealing. Extended X-ray absorption fine structure measurements revealed the existence of oxygen vacancies in the local structure surrounding zirconium for all films. However, the amount of these oxygen vacancies was found to be significantly higher for the amorphous films as compared to that for the films in the cubic phase (660 nm as-deposited and 140 nm annealed films). The stabilization of the cubic phase is attributed to the breaking of the oxygen-zirconium bonds due to the presence of the oxygen vacancies, which results in the suppression of the soft X2- mode of vibration of the oxygen sub-lattice. Our first-principles modeling under the framework of density functional theory shows that the cubic structure with oxygen vacancies is indeed more stable under ambient conditions than its pristine (without vacancies) counterpart due to breaking of the oxygen bonds. The requirement of a critical amount of these vacancies for cubic phase stabilization is discussed.

Defect-induced photoluminescence from gallium-doped zinc oxide thin films: influence of doping and energetic ion irradiation.

Herein, we present defect-induced photoluminescence behavior of Ga-doped ZnO (GZO) thin films with varying doping (Ga) concentrations and energetic ion irradiation. The Ga-doped ZnO thin films were prepared by a sol-gel spin-coating method. Micro-photoluminescence (µ-PL) was carried out to investigate the defect-related emission with the variation of doping concentration and ion irradiation. The PL spectra revealed that all films showed near-band-edge (NBE) emission along with a broad visible emission band, consisting of violet, blue, green, and yellow emission bands. The intensity of these emission bands was found to be strongly dependent on the Ga doping concentration and ion irradiation. Interestingly, a pronounced violet emission band around 2.99 eV (415 nm) was observed for the Ga-doped ZnO thin films with high Ga doping concentration, whereas an irradiated film with high ion fluence exhibited a strong green emission around 2.39 eV (519 nm); however, we concluded that the violet emission might have originated from zinc interstitial defects (Zni), and the concentration of Zni increased with the increasing doping concentration. The green emission is ascribed to the oxygen vacancies (VO), and the concentration of the VO defects increases with the increasing ion fluence. Thus, the µ-PL spectra of the irradiated films with emission dominating in the blue and green regions could be attributed to the formation of extended defects such as clusters and ionizing centers of Zni and VO. Herein, an in-depth understanding of the variation in defects related to the emission bands from these films is reported and correlated with the transport properties of these films for their possible optoelectronic applications.

Self-assembled nano-dots structures on Si(111) surfaces by oblique angle sputter-deposition.

Controlled surface modification and nano-dots structures over Si(111) surfaces have been produced by oblique angle sputter deposition of 80 keV Ar+ beam. Temporal parameters such as self-assemble, tunability of size and density of fabricated nano-dots exhibit distinct fluence dependence. Crystalline to amorphous (c/a) phase transition for sputter deposited Si(111) surfaces has been observed. RBS/C reveals the non-linear response of damage distribution with Ar ion fluence. Compositional alterations like degree of amorphization, damage distribution and depth profiling of Ar in these nano-structured surfaces has been correlated with the morphological and structural findings. The underlying self-organization mechanism relies in ion beam sputtering induced erosion and re-deposition of Si atoms thereby leading to mass transport inside the amorphous layers. Such nano-structured Si(111) surfaces could be applied as key engineering substrates for surface reconstruction, optoelectronic devices, data storage devices, recording media and photovoltaic applications.

Fabrication and characterization of carbon-backed thin 208Pb targets.

Thin carbon-backed isotopically enriched 208Pb targets were required for our experiment aimed to study the reaction dynamics for 48Ti + 208Pb system, populating the near super-heavy nucleus 256Rf, through mass-energy correlation of the fission fragments. Purity and thickness of the targets are of utmost importance in such studies as these factors have strong influence on the measurement accuracy of mass and energy distribution of fission fragments. 208Pb targets with thickness ranging from 60 µg/cm2 to 250 µg/cm2 have been fabricated in high vacuum environment using physical vapor deposition method. Important points in the method are as follows: •208Pb was deposited using resistive heating method, whereas carbon (backing foil) deposition was performed by using the electron beam bombardment technique.•Different characterization techniques such as Particle Induced X-ray Emission (PIXE), Energy Dispersive X-Ray Fluorescence (EDXRF) and Rutherford Backscattering Spectrometry (RBS) were used to assert the purity and thickness of the targets.•These targets have successfully been used to accomplish our experimental objectives.

Production of dioxygen in the dark: dismutases of oxyanions.

O2-generating reactions are exceedingly rare in biology and difficult to mimic synthetically. Perchlorate-respiring bacteria enzymatically detoxify chlorite (ClO2(-) ), the end product of the perchlorate (ClO(4)(-) ) respiratory pathway, by rapidly converting it to dioxygen (O2) and chloride (Cl(-)). This reaction is catalyzed by a heme-containing protein, called chlorite dismutase (Cld), which bears no structural or sequence relationships with known peroxidases or other heme proteins and is part of a large family of proteins with more than one biochemical function. The original assumptions from the 1990s that perchlorate is not a natural product and that perchlorate respiration might be confined to a taxonomically narrow group of species have been called into question, as have the roles of perchlorate respiration and Cld-mediated reactions in the global biogeochemical cycle of chlorine. In this chapter, the chemistry and biochemistry of Cld-mediated O2generation, as well as the biological and geochemical context of this extraordinary reaction, are described.

A study on the consequence of swift heavy ion irradiation of Zn-silica nanocomposite thin films: electronic sputtering.

Zn-silica nanocomposite thin films with varying Zn metal content, deposited by atom beam sputtering technique were subjected to 100 MeV Ag ion irradiation. Rutherford backscattering spectrometry reveals the loss of Zn with irradiation, which is observed to be greater from thin films with lower Zn content. The sputtered species collected on carbon-coated transmission electron microscopy (TEM) grids consist of Zn nanoparticles of sizes comparable to those present in the nanocomposite thin film. The process of size-dependent electronic sputtering of Zn is explained on the basis of an inelastic thermal spike model. The possibility of direct cluster emission is explained by pressure spike built inside the track, initiated by a temperature spike.

Synthesis of Pt nanoparticles and their burrowing into Si due to synergistic effects of ion beam energy losses.

We report the synthesis of Pt nanoparticles and their burrowing into silicon upon irradiation of a Pt-Si thin film with medium-energy neon ions at constant fluence (1.0 × 10(17) ions/cm(2)). Several values of medium-energy neon ions were chosen in order to vary the ratio of the electronic energy loss to the nuclear energy loss (S e/S n) from 1 to 10. The irradiated films were characterized using Rutherford backscattering spectroscopy (RBS), atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). A TEM image of a cross section of the film irradiated with S e/S n = 1 shows ≈5 nm Pt NPs were buried up to ≈240 nm into the silicon. No silicide phase was detected in the XRD pattern of the film irradiated at the highest value of S e/S n. The synergistic effect of the energy losses of the ion beam (molten zones are produced by S e, and sputtering and local defects are produced by S n) leading to the synthesis and burrowing of Pt NPs is evidenced. The Pt NP synthesis mechanism and their burrowing into the silicon is discussed in detail.

How pH modulates the reactivity and selectivity of a siderophore-associated flavin monooxygenase.

Flavin-containing monooxygenases (FMOs) catalyze the oxygenation of diverse organic molecules using O2, NADPH, and the flavin adenine dinucleotide (FAD) cofactor. The fungal FMO SidA initiates peptidic siderophore biosynthesis via the highly selective hydroxylation of L-ornithine, while the related amino acid L-lysine is a potent effector of reaction uncoupling to generate H2O2. We hypothesized that protonation states could critically influence both substrate-selective hydroxylation and H2O2 release, and therefore undertook a study of SidA's pH-dependent reaction kinetics. Consistent with other FMOs that stabilize a C4a-OO(H) intermediate, SidA's reductive half reaction is pH independent. The rate constant for the formation of the reactive C4a-OO(H) intermediate from reduced SidA and O2 is likewise independent of pH. However, the rate constants for C4a-OO(H) reactions, either to eliminate H2O2 or to hydroxylate L-Orn, were strongly pH-dependent and influenced by the nature of the bound amino acid. Solvent kinetic isotope effects of 6.6 ± 0.3 and 1.9 ± 0.2 were measured for the C4a-OOH/H2O2 conversion in the presence and absence of L-Lys, respectively. A model is proposed in which L-Lys accelerates H2O2 release via an acid-base mechanism and where side-chain position determines whether H2O2 or the hydroxylation product is observed.

The Structure-Function Linkage Database.

The Structure-Function Linkage Database (SFLD, http://sfld.rbvi.ucsf.edu/) is a manually curated classification resource describing structure-function relationships for functionally diverse enzyme superfamilies. Members of such superfamilies are diverse in their overall reactions yet share a common ancestor and some conserved active site features associated with conserved functional attributes such as a partial reaction. Thus, despite their different functions, members of these superfamilies 'look alike', making them easy to misannotate. To address this complexity and enable rational transfer of functional features to unknowns only for those members for which we have sufficient functional information, we subdivide superfamily members into subgroups using sequence information, and lastly into families, sets of enzymes known to catalyze the same reaction using the same mechanistic strategy. Browsing and searching options in the SFLD provide access to all of these levels. The SFLD offers manually curated as well as automatically classified superfamily sets, both accompanied by search and download options for all hierarchical levels. Additional information includes multiple sequence alignments, tab-separated files of functional and other attributes, and sequence similarity networks. The latter provide a new and intuitively powerful way to visualize functional trends mapped to the context of sequence similarity.

Synthesis of cobalt nanoparticles on Si (100) by swift heavy ion irradiation.

We report the growth and characterization of uniform-sized nanoparticles of cobalt on n-type silicon (100) substrates by swift heavy ion (SHI) irradiation. The Co thin films of 25-nm thicknesses were grown by e-beam evaporation and irradiated with two different types of ions, 45-MeV Li3+ and 100-MeV O7+ ions with fluences ranging from 1 × 1011 to 1 × 1013 ions/cm2. SHI irradiation, with the beam rastered over the area of the film, resulted in the restructuring of the film into a dense array of Co nanostructures. Surface topography studied by atomic force microscopy revealed narrowed size distributions, with particle sizes ranging from 20 to 50 nm, formed through a self-organized process. Ion fluence-dependent changes in crystallinity of the Co nanostructures were determined by glancing angle X-ray diffraction. Rutherford backscattering spectroscopy analysis showed the absence of beam-induced mixing in this system. Surface restructuring and beam-induced crystallization are the dominant effects, with the nanoparticle size and density being dependent on the ion fluence. Results are analyzed in the context of molecular dynamics calculations of electron-lattice energy transfer.

The chlorite dismutase (HemQ) from Staphylococcus aureus has a redox-sensitive heme and is associated with the small colony variant phenotype.

The chlorite dismutases (C-family proteins) are a widespread family of heme-binding proteins for which chemical and biological roles remain unclear. An association of the gene with heme biosynthesis in Gram-positive bacteria was previously demonstrated by experiments involving introduction of genes from two Gram-positive species into heme biosynthesis mutant strains of Escherichia coli, leading to the gene being renamed hemQ. To assess the gene product's biological role more directly, a Staphylococcus aureus strain with an inactivated hemQ gene was generated and shown to be a slow growing small colony variant under aerobic but not anaerobic conditions. The small colony variant phenotype is rescued by the addition of exogenous heme despite an otherwise wild type heme biosynthetic pathway. The ΔhemQ mutant accumulates coproporphyrin specifically under aerobic conditions. Although its sequence is highly similar to functional chlorite dismutases, the HemQ protein has no steady state reactivity with chlorite, very modest reactivity with H2O2 or peracetic acid, and no observable transient intermediates. HemQ's equilibrium affinity for heme is in the low micromolar range. Holo-HemQ reconstituted with heme exhibits heme lysis after <50 turnovers with peroxide and <10 turnovers with chlorite. The heme-free apoprotein aggregates or unfolds over time. IsdG-like proteins and antibiotic biosynthesis monooxygenases are close sequence and structural relatives of HemQ that use heme or porphyrin-like organic molecules as substrates. The genetic and biochemical data suggest a similar substrate role for heme or porphyrin, with possible sensor-regulator functions for the protein. HemQ heme could serve as the means by which S. aureus reversibly adopts an SCV phenotype in response to redox stress.