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.

Ubiquitous organic molecule-based free-standing nanowires with ultra-high aspect ratios.

The critical dimension of semiconductor devices is approaching the single-nm regime, and a variety of practical devices of this scale are targeted for production. Planar structures of nano-devices are still the center of fabrication techniques, which limit further integration of devices into a chip. Extension into 3D space is a promising strategy for future; however, the surface interaction in 3D nanospace make it hard to integrate nanostructures with ultrahigh aspect ratios. Here we report a unique technique using high-energy charged particles to produce free-standing 1D organic nanostructures with high aspect ratios over 100 and controlled number density. Along the straight trajectory of particles penetrating the films of various sublimable organic molecules, 1D nanowires were formed with approximately 10~15 nm thickness and controlled length. An all-dry process was developed to isolate the nanowires, and planar or coaxial heterojunction structures were built into the nanowires. Electrical and structural functions of the developed standing nanowire arrays were investigated, demonstrating the potential of the present ultrathin organic nanowire systems.

Localized Surface Plasmon Resonance Studies on Pd/C Nano-Composite System: Effect of Metal Concentration and Annealing Temperature.

The effects of metal concentration and annealing temperature on the localized surface plasmon resonance (LSPR) properties of the Pd nanoparticles (NP) dispersed in carbon were investigated. The Pd/C nano-composite thin films with 7 to 39 atomic % concentration of metal content were deposited using the atom beam co-sputtering techniques and subjected to annealing at temperature varying from 300 °C to 600 °C. The UV-vis spectroscopy studies on as-prepared films displayed a Mie scattering profile, but not well-defined LSPR bands were observed for all the values of Pd concentration. This is attributed to the smaller size (3-4 nm) of Pd NPs and rough Pd/C interface, as confirmed from TEM studies. When samples were annealed at a temperature of 300 °C, three broad LSPR absorption bands in the visible region, along with a sharp peak at 210 nm, were observed and the effect of Pd concentration variation was insignificant on their position. The multiple LSPR bands were observed due to agglomeration NPs, which is consistent with earlier reports and is also observed in the TEM images. When annealing temperature was subsequently increased to 500 °C, a blue shift in the LSPR peak position with an increase in the Pd concentration was observed, which phenomena is attributed to the formation of bigger NPs with the formation of sharp NPs-interface at high temperature upon annealing. A monotonic increase in the magnitude and decrease in the FWHM with an increase in concentration suggested change in the dielectric function of sample due to the growth of NPs. This is further confirmed from XRD studies, where strain relaxation and grain growth were observed. The intensity of the SPR peak decreased with an increase in the annealing temperature. The LSPR peak disappeared on annealing at a temperature of 600 °C, suggesting the formation of continuous polycrystalline thin films of Pd. In summary, NPs size, metalmatrix interface, and concentration of metal play key roles in the tailoring the LSPR properties of the Pd.

Voltammetric measurements of neurotransmitter-acetylcholine through metallic nanoparticles embedded 2-D material.

The most generally spread neurotransmitter acetylcholine (Ach) is used as a chemical messenger assisting in conveying signals transversely through the nerve synapse. Herein, two enzymes acetylcholinesterase and choline oxidase were covalently immobilized over the gold nanoparticles (AuNPs) embedded graphene oxide (GO; 2D carbon material) nanocomposite modified ITO coated glass plate. The synergetic and unique properties of AuNPs and GO present in nanocomposite are used to detect the ultra-small concentration of analyte, Ach. The prepared nanocomposites were characterized using different techniques i.e. TEM, XRD, SEM, FTIR, UV-Vis and Raman Spectroscopy. All the electrochemical measurements were performed using 3 electrodes integrated electrochemical system by introducing Ach through varying its concentration from 100 pM to 1000 nM. Cyclic voltammetry curves for different concentrations of Ach indicate the facile charge transfer process over the working electrode. Square wave voltammetry curves indicate the good sensing measurements of the modified electrode at the fixed potential. The limit of detection was found to be as low as 100 pM. In addition to these, selectivity of the electrode towards Ach molecule was confirmed by measuring the response towards other interfering agents. Besides this, the present nano interface is capable of detecting Ach in biological fluid such as serum.

Assessing a thermal spike model of swift heavy ion-matter interactions via Pd1-xNix/Si interface mixing.

The thermal spike model (TSM), a widely accepted mechanism of swift heavy ion (SHI)-matter interactions, provides explanation for various SHI induced effects, including mixing across interfaces. We assess the validity of the model via tuning the electron-phonon coupling strength (G) by taking a series Pd1-xNix of a completely solid soluble binary, and then observing Pd1-xNix/Si interface mixing induced by a combination of 100 MeV Au ion irradiation and 4 keV Ar ion sputtering. If the TSM truly describes the SHI-matter interaction mechanism, any non-linearity in x-variation of G must also result in a similar non-linearity in the x-dependence of mixing. Experimentally, the extent of mixing has been parametrized by the irradiation induced change Δσ2 in variances of Pd and Ni depth profiles derived from XPS. Computationally, G determined using density functional theory has been used to solve the equations appropriate to the TSM, and then an equivalent quantity L2, proportional to Δσ2, has been calculated. Both Δσ2(x) and L2(x) show non-linearities, albeit in slightly dissimilar ways, leading to a conjecture that the present work at least does not invalidate the TSM.

Enhanced room temperature ferromagnetism and green photoluminescence in Cu doped ZnO thin film synthesised by neutral beam sputtering.

The Cu (3 to 15 at%) is incorporated into ZnO thin film by atomic beam co-sputtering has been investigated for enhancement in room temperature ferromagnetism and green photo-luminance. These Cu-ZnO thin films examined with Raman spectroscopy, X-Ray Diffraction (XRD), UV-Visible spectroscopy, Hall measurement, magnetic force microscopy (MFM) and magnetic hysteresis. Raman spectroscopy, XRD confirms wurtzite structure and improvement in the crystallinity of ZnO upto 7% Cu. Further increase in Cu concentration results in growth in Cu nanoparticles. On increasing Cu concentration, there is decrement in transparency and increase in band gap with increase in n-type carrier concentration as confirmed from UV-Visible and Hall measurement studies. Magnetic measurement exhibited unique feature of room temperature ferromagnetic ordering in undoped and doped sample upto 3% Cu. The enhancement in magnetic moment as well as green emission in photoluminescence response with increase in Cu doping indicates that generation of large defects in ZnO by Cu doping, which can be attributed to combined effect of the presence of oxygen vacancies and/or structural inhomogeneity as well as formation of bound magnetic polarons. Importantly, synthesised Cu doped ZnO thin films can be used as spin LEDs and switchable spin-laser diodes.

Generation and application of LET calibration curve for neutron dosimetry using CR-39 detector and microwave induced chemical etching.

Microwave induced chemical etching (MICE) has been established as a faster and improved technique compared to other contemporary etching techniques for the development of tracks in a CR-39 detector. However, the methodology could not be applied for LET (linear energy transfer) spectrometry due to lack of a calibration curve using this method. For this purpose, a new LET calibration curve in the range of 12 keV/µm-799 keV/µm was generated considering different ions such as H, Li, C, O, and F on CR-39 having different LETs in water. An empirical relation was established from the obtained calibration curve for determining the value of LET (in water) from the value of V, the ratio of track etch rate to bulk etch rate. For application of this calibration curve in neutron dosimetry, CR-39 detectors were irradiated to neutrons generated from 120 and 142 MeV 16O+27Al systems followed by a similar MICE procedure. The absorbed dose (DLET) and the dose equivalent (HLET) were obtained from the LET spectra and were found to be 13% and 10% higher for 142 MeV 16O+27Al system than those for 120 MeV 16O+27Al system, respectively. The outcome of the study demonstrates the possibility of using the MICE technique for neutron dose estimation by CR-39 via LET spectrometry.

Mesoporous polyaniline nanofiber decorated graphene micro-flowers for enzyme-less cholesterol biosensors.

In the present work, we have studied a nanocomposite of polyaniline nanofiber-graphene microflowers (PANInf-GMF), prepared by an in situ rapid mixing polymerization method. The structural and morphological studies of the nanocomposite (PANInf-GMF) were carried out by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FTIR) and Raman spectroscopy. The mesoporous, nanofibrous and microflower structures were observed by scanning electron microscopy. The functional groups and synergetic effects were observed by FTIR and micro-Raman measurements. The water wettability was carried out by a contact angle measurement technique and found to be super hydrophilic in nature towards water. This nanocomposite was deposited onto indium-tin-oxide coated glass substrate by a drop casting method and used for the detection of cholesterol using an electrochemical technique. The differential pulse voltammetry studies show the appreciable increase in the current with the addition of 1.93 to 464.04 mg dl(-1) cholesterol concentration. It is also found that the electrodes were highly selective towards cholesterol when compared to other biological interfering analytes, such as glucose, urea, citric acid, cysteine and ascorbic acid. The sensitivity of the sensor is estimated as 0.101 µA mg(-1) dl cm(-2) and the lower detection limit as 1.93 mg dl(-1). This work will throw light on the preparation of non-enzymatic biosensors based on PANInf-carbon nanostructure composites.

Unraveling The Origin of Enhanced Field Emission from Irradiated FeCo-SiO2 Nanocomposites: A Combined Experimental and First-Principles Based Study.

This work is driven by the vision of engineering planar field emitters with ferromagnetic metal-insulator nanocomposite thin films, using swift heavy ion (SHI) irradiation method. FeCo nanoparticles inside SiO2 matrix, when subjected to SHI get elongated. Using this, we demonstrate here a planar field emitter with maximum current density of 550 µA/cm(2) at an applied field of 15 V/µm. The film, irradiated with 5 × 10(13) ions/cm(2) fluence (5e13) of 120 MeV Au(9+) ions, shows very high electron emitting quantum efficiency in comparison to its unirradiated counterpart. Surface enhanced Raman spectroscopy analysis of unirradiated and 5e13 films further confirms that the field emission (FE) enhancement is not only due to surface protrusions but also depends on the properties of entire matrix. We find experimental evidence of enhanced valence band density of states (VB DOS) for 5e13 film from XPS, which is verified in the electronic structure of a model FeCo cluster from first-principles based calculations combining density functional theory (DFT) and molecular dynamics (MD) simulations. The MD temperature is selected from the lattice temperature profile inside nanoparticles as deduced from thermal spike model. Increasing the irradiation fluence beyond 5e13, results in reduced VB DOS and melting of surface protrusions, thus causing reduction of FE current density. We finally conclude from theoretical analysis that change in fluence alters the co-ordination chemistry followed by the charge distribution and spin alignment, which influence the VB DOS and concurrent FE as evident from our experiment.

Effects of swift heavy ion irradiation on structural, optical and photocatalytic properties of ZnO-CuO nanocomposites prepared by carbothermal evaporation method.

ZnO-CuO nanocomposite thin films were prepared by carbothermal evaporation of ZnO and Cu, combined with annealing. The effects of 90 MeV Ni(7+) ion irradiation on the structural and optical properties of ZnO-CuO nanocomposites were studied by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), UV-visible absorption spectroscopy and Raman spectroscopy. XRD studies showed the presence of ZnO and CuO nanostructures in the nanocomposites. FESEM images revealed the presence of nanosheets and nanorods in the nanocomposites. The photocatalytic activity of ZnO-CuO nanocomposites was evaluated on the basis of degradation of methylene blue (MB) and methyl orange (MO) dyes under sun light irradiation and it was observed that swift heavy ion irradiation results in significant enhancement in the photocatalytic efficiency of ZnO-CuO nanocomposites towards degradation of MB and MO dyes. The possible mechanism for the enhanced photocatalytic activity of ZnO-CuO nanocomposites is proposed. We attribute the observed enhanced photocatalytic activity of ZnO-CuO nanocomposites to the combined effects of improved sun light utilization and suppression of the recombination of photogenerated charge carriers in ZnO-CuO nanocomposites.

Effect of grain size and microstructure on radiation stability of CeO2: an extensive study.

To investigate the variation in the radiation stability of ceria with microstructure under the electronic excitation regime, ceria samples sintered under different conditions were irradiated with high energy 100 MeV Ag ions. The ceria nanopowders were synthesized and sintered at 800 °C (S800), 1000 °C (S1000) and 1300 °C (S1300), respectively. The samples with widely varying grain size, densities and microstructure were obtained. The pristine and irradiated samples were studied by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). None of the samples amorphized up to the highest fluence of 1 × 10(14) ions per cm(2) employed in this study. XRD and Raman studies showed that the sample with lowest grain size suffered maximum damage while the sample with largest grain size was most stable and showed little change in crystallinity. Raman spectroscopy indicated the enhanced formation of Ce(3+) and related defects in the sample with larger grain size after irradiation. The most intriguing result was the absence of Ce(3+)-related defects in the sample with lowest grain size which actually showed maximum damage upon irradiation. The XPS studies on S800 and S1300 provided concrete evidence for the presence of Ce(3+) and oxygen ion vacancies in S1300. The grain boundaries and grain size dependent stability have been discussed.

Shape elongation of Zn nanoparticles in silica irradiated with swift heavy ions of different species and energies: scaling law and some insights on the elongation mechanism.

Zinc nanoparticles (NPs) embedded in silica were irradiated with swift heavy ions (SHIs) of seven different combinations of species and energies. The shape elongation induced by the irradiations was evaluated by optical linear dichroism (OLD) spectroscopy, which is a sensitive tool for determining the change in the mean aspect ratio (AR) of NPs. Although the mean AR change indicated a linear fluence dependence in the low- and medium-fluence regions, it indicated a nonlinear dependence in the high-fluence region. The data reveal that the elongation efficiency of Zn is correlated with the electronic stopping power 'Se in silica' and is not correlated with either the 'Se in Zn' or the nuclear stopping power. The elongation efficiency plotted as a function of the 'Se in silica' revealed a linear relationship, with a threshold value of ∼2 keV nm(-1), which is the same dependence exhibited by the ion-track formation in silica. The log-log plot showed that the elongation efficiency increased linearly with Se above a critical value of ∼3 keV nm(-1) and steeply decreased with Se to the power of 5 below the critical Se. The steep decrease can be ascribed to the discontinuous nature of the ion tracks, which is expected at Se ∼ 2-4 keV nm(-1) in silica. The fluence Φ dependences of AR - 1 under various irradiations are well-normalized with the electronic energy deposition of SHIs, i.e., the product of Se and Φ, with a Se greater than the same critical value of ∼3 keV nm(-1). The normalized data above the critical value fell on a linear relation, AR(Φ) - 1 ∝ SeΦ, for SeΦ < 2 keV nm(-3) and a sublinear relation, AR(Φ) - 1 ∝ (SeΦ)(1/2) for SeΦ > 2 keV nm(-3). On the basis of these experimental results, we discuss some insights into the elongation mechanism.

Structure-modified stress dynamics and wetting characteristics of carbon nanotubes and multilayer graphene for electron field emission investigations.

In the present work, feasibility of achieving enhanced electron field-emission properties of stress-induced carbon nanotubes (CNTs) and multilayer graphene (MLGs) by ion modification is studied. Micro-Raman spectroscopy is used as a potent technique for in-depth investigations of stress-induced CNTs and MLGs. It is found that iron used as a catalyst, compresses at particular fluence and induces stresses in CNTs and MLGs to modify these structures, supported by high-resolution transmission electron microscopy (HRTEM) studies. The stresses are explained by the buckling wavelength (λ ∝ e((r/t)0.5)). Furthermore, the stresses induced in exotic nanostructures are studied for investigating wetting properties, which are well-corroborated with electron emission characteristics. It is found out that less-wetted CNTs and MLGs display enhanced emission properties with turn-on voltages (Eon) of 1.5 and 2.1 V/µm, respectively, in comparison to hydrophilic CNTs and MLGs with Eon of 2.6 and 4 V/µm, respectively.

Synthesis of embedded Au nanostructures by ion irradiation: influence of ion induced viscous flow and sputtering.

The ion-irradiation induced synthesis of embedded Au nanoparticles (NPs) into glass from islands of Au on a glass substrate is studied in the context of recoiling atoms, sputtering and viscous flow. Cross sectional transmission electron microscopy studies revealed the formation of Au NPs embedded in the glass substrates by the 50 keV Si(-) ion irradiation of irregularly shaped Au nanostructures on the glass surfaces at a fluence of 3 × 10(16) ions/cm(2). The depth profiles of Au in the samples were obtained from high-resolution Rutherford backscattering spectrometry studies. The results from TRIDYN simulation reveal the role of various ion-induced processes during the synthesis of the embedded Au NPs, viz. sputtering and recoiling atoms. Simulation and experimental results suggest that the viscous flow is one of the major factors that are responsible for the embedding of Au nanoparticles into the glass substrate.

Studies on carbon nanotubes and fullerenes under extreme conditions.

Ion beam irradiation of materials can cause defect creation as well as defect annealing depending on the ion beam parameters such as ion fluence and the energy loss of ions in materials. In present review, we report the behaviour of carbon nanotubes under exteme conditions such as laser irradiation and ion irradiation. The reorientation of the crystalline planes in confined single crystal nickel nanorods inside carbon nano tube, induced by heavy ion irradiation, is reported. Axial buckling of nickel nanorods as well as walls of carbon nano tubes in nickel encapsulated carbon nano tubes under swift heavy ion irradiation at high fluence is observed. At high fluence, amorphization of nickel nanorods inside carbon nanotubes is also observed. Axial buckling and amorphization under ion irradiation at high fluence are dependent on the number of walls in carbon nanotubes. High resolution transmission electron microscopy was used to investigate the reorientations, buckling and amorphization of metal filled nanotubes. Synthesis of carbon nanowires by ion irradiation of fullerene and their field emission properties with comparison to that of unirradiated and irradiated carbon nanotubes are reported. An international scenario with future prospects of ion beam studies in carbon nanotube is briefed.

Synthesis of plasmonic nanocomposites for diverse applications.

We report the synthesis of gold and silver nanostructures embedded in different dielectric matrices by atom beam co-sputtering, a novel technique. We have synthesized gold-silicon core shell nanostructures and Au-ZnO nanocomposite with tunable surface plasmon resonance (SPR) by atom beam co-sputtering and subsequent annealing. The Au-ZnO nanocomposite shows significant enhancement in intensity of Raman modes of fullerene molecules and therefore can help in surface enhanced Raman spectroscopy investigation of organic molecules. The synthesized Ag-polymer nanocomposite thin films show excellent features of broad SPR absorption extending upto IR region and a narrow transmission of light in UV region approximately 320 nm which could be of technological interest in solar absorbers and UV light filters respectively. The Ag-silica nanocomposite thin films show their utility in glucose sensing. The gold-silica nanocomposite thin films exhibit their possible use in detection of human ovarian cancer cells in a preliminary study. The shift in SPR peak of Au nanoparticles (NPs) present at the surface of silica synthesized by thermal evaporation and annealing, after attachment of biological molecules like proteins has been studied.

Synthesis and characterization of Ag-polymer nanocomposites.

We report the synthesis of Ag nanoparticles in polyethylene terephthalate (PET) matrix using atom beam co-sputtering. Metal filling factor was evaluated by Rutherford backscattering spectrometry. Microstructural evolutions of the nanocomposites films were investigated by transmission electron microscopy, which confirmed the formation of irregular shaped Ag nanoparticles. The X-ray photoelectron spectroscopy measurements of the sputter deposited PET film and co-sputtered deposited Ag-PET as well as PET bulk foil (from Goodfellows) were performed to study chemical composition of the nanocomposite films. The optical properties of these nanocomposites were studied by light absorption/transmission, which revealed a narrow transmission of UV light approximately 320 nm and a broad surface plasmon resonance absorption extending up to infrared region (approximately 2400 nm). Swift heavy ion irradiation of Ag-PET nanocomposite resulted in narrowing the full width at half maximum of transmission band.

Swift heavy ions for controlled modification of soft magnetic properties of Fe0.85N0.15 thin film.

It is shown that the soft magnetic properties of amorphous Fe0.85N0.15 film can be modified in a controlled manner by irradiation with 120 MeV Ag ions. Irradiation causes relaxation of short range as well as long range stresses, resulting in an improvement in the soft magnetic properties. Nuclear resonance reflectivity has been used to measure the diffusion length of Fe atoms as a function of irradiation fluence. It is found that the atomic motion associated with irradiation is not expected to modify significantly the interfaces with substrate or other layers.

KeV ion-induced effective surface modifications on InP.

In the present study, we have analyzed the changes in surface morphology leading to formation of periodic structures known as ripples which arise due to an interplay between sputtering and surface diffusion. The 1.5 keV Ar atoms with a flux of 14.8 mA/cm2 are used in the present study. The InP(100) samples were bombarded at an incidence angle of 45 degrees to the normal at a base pressure of 1 x 10(-6) Torr at room temperature with fluences varying from 4 x 10(16) to 3.2 x 10(17) atoms/cm2. The rippled InP(100) surface was characterized with AFM. An increase in the ripple wavelengths, from 60 nm to 150 nm with the fluence has been observed. The width of the ripples varies from 38 nm to 128 nm and ripple amplitude varies from 0.8 nm to 16 nm with increasing fluence. One can control the dimension of the ripples in nano scale by controlling the fluence. Scaling studies have been performed to understand the mechanism responsible for such kind of surface evolution. The roughness parameter, alpha was found to be between 0.65 to 0.75 and the growth parameter, beta, as 1.14 +/- 0.12. The XPS characterization has also been employed to study the changes in the behavior of the InP with varying fluence.

Surface plasmon resonance of Ag nanoparticles embedded in partially oxidized amorphous Si matrix.

Nanocomposite films containing Ag nanoparticles embedded in partially oxidized amorphous Si matrix were deposited on silica glass substrates by co-sputtering of Ag and Si with 1.5 keV neutral Ar atoms. The Ag content and thickness of the nanocomposite films was determined by Rutherford backscattering spectrometry. Optical absorption studies revealed the presence of surface plasmon resonance (SPR) indicating the formation of Ag nanoparticles in the as-deposited films. The position, width and strength of SPR have been found to be strongly dependent on the Ag content of the films. For annealing in oxidizing atmosphere, a significant red shift in the SPR along with a drastic reduction in the resonant absorption has been observed. The amount of red shift has been found to be dependent on the Ag content of the films. Transmission electron microscopy was used to study the size distribution, shape and crystal structure of Ag nanoparticles in the nanocomposite films. TEM analysis of annealed sample revealed the formation of silver oxide nanoshells surrounding Ag nanoparticles.