Rutherford Backscattering Spectrometry Results Research Articles

Low energy ion irradiation induced Au/Ag multilayer nanostructured substrates for SERS-based molecular sensing

Au and Ag are the most prominent plasmonic materials to study Surface-Enhanced Raman Spectroscopy (SERS) because of their wide tuning of localized surface plasmon resonance in the broad wavelength range. In the present work, the formation of nanostructures of Au single-layer, Au/Ag bi-layer, and Au/Ag/Au/Ag four-layer thin films on silicon substrates by low energy Kr++ ion irradiation with fluences of 1 × 1015 and 3 × 1015 ions/cm2 was systematically studied and were used for the detection of dye molecules. The surface morphology and microstructural analysis indicated the formation of different nanostructures with different ion fluences by atomic force microscopy and field emission scanning electron microscopy. Rutherford backscattering spectrometry results indicate a considerable change in film thickness after ion irradiation, mainly due to the removal of surface atoms due to sputtering. The maximum enhancement in Raman intensity of R6G was observed in the Bi-layer Au–Ag substrate compared to other substrates with an enhancement factor of 4.78 × 106 corresponding to a 1516 cm−1 characteristic peak in SERS analysis. Coumarin 343 molecules trace amount were detected to determine the versatility of the substrate. A finite-difference time-domain simulation was performed to provide a better understanding of the nanostructure hot-spots formation and support the obtained SERS results.

Solid-state reactions between iridium thin films and silicon carbide in the 700 °C to 1000 °C temperature range

The solid-state reactions between iridium thin films (50 nm) and 6H‐SiC in the 700–1000 °C temperature range were investigated. The microstructure and surface morphology of the Ir thin films on 6H‐SiC were examined using Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), Raman spectroscopy and grazing incidence X-ray diffraction (GIXRD). The electron beam deposited Ir films had a polycrystalline structure with the (111) preferred orientation and their crystallinity increased with annealing temperature. The Ir films were stable and did not interact with the SiC substrate after annealing at temperatures below 800 °C. The RBS results indicate that the initial reaction at 800 °C was very fast and almost the entire 50 nm film had reacted leading to the formation of Ir-rich silicides, Ir3Si2 and IrSi. After annealing at 900 and 1000 °C, the RBS profiles XRD results showed that the solid-state reactions proceeded further and Ir3Si2 was converted to IrSi. At the final annealing temperature of 1000 °C the predominant phase was IrSi. Thermodynamic analysis of the reaction phases confirmed the formation and sequence of the phases observed.

Swift Heavy Ion-Induced Reactivity and Surface Modifications in Indium Thin Films.

As an energetic ion traverses a target material, it loses its energy through the processes of electronic energy loss (Se) and nuclear energy loss (Sn). Controlled swift heavy ion (SHI) irradiation on solid targets produces its effects through both of these mechanisms, as a consequence of which modifications occur in the structure, surface morphology, and magnetic and optical properties, apart from ion implantation and ion-induced reactivity. A systematic investigation of these effects can be useful in developing standard protocols for creating desired effects in materials using specific ion beams. In this study, indium films of thickness 25 nm were deposited on silicon substrates and were subjected to 100 MeV O7+ and 100 MeV Si7+ ion irradiation, with the fluences varying from 1 × 1011 to 1 × 1013 ions/cm2. The pristine and SHI-irradiated films were then characterized using glancing incidence X-ray diffraction (GIXRD), Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The motive was to identify the effects of irradiation with different ion species having large variations in electronic and nuclear energy losses. While the RBS results suggest that sputtering is extremely low and that there are no major changes in the film composition due to ion beam-induced mixing, the GIXRD analysis indicates that increasing the ion fluence reduces the crystallinity of the film for both the ions. Ion beam irradiation with O7+ ions, however, results in beam-induced reactivity, as the GIXRD scan shows characteristic peaks from indium oxide (In2O3), which become the predominant peaks at the highest fluence used here. Si7+ ion irradiation results in a narrowing of the particle size distribution on the surface, with no evidence of reactivity. SEM results indicate fusion and fragmentation of grains with the increase in the ion fluences, and AFM images reveal an increase in the surface roughness of a few percent when irradiated with both 100 MeV O7+ and 100 MeV Si7+ ions.

Chemical Vapor Deposited Mixed Metal Halide Perovskite Thin Films.

In this article, we used a two-step chemical vapor deposition (CVD) method to synthesize methylammonium lead-tin triiodide perovskite films, MAPb1−xSnxI3, with x varying from 0 to 1. We successfully controlled the concentration of Sn in the perovskite films and used Rutherford backscattering spectroscopy (RBS) to quantify the composition of the precursor films for conversion into perovskite films. According to the RBS results, increasing the SnCl2 source amount in the reaction chamber translate into an increase in Sn concentration in the films. The crystal structure and the optical properties of perovskite films were examined by X-ray diffraction (XRD) and UV-Vis spectrometry. All the perovskite films depicted similar XRD patterns corresponding to a tetragonal structure with I4cm space group despite the precursor films having different crystal structures. The increasing concentration of Sn in the perovskite films linearly decreased the unit volume from about 988.4 Å3 for MAPbI3 to about 983.3 Å3 for MAPb0.39Sn0.61I3, which consequently influenced the optical properties of the films manifested by the decrease in energy bandgap (Eg) and an increase in the disorder in the band gap. The SEM micrographs depicted improvements in the grain size (0.3–1 µm) and surface coverage of the perovskite films compared with the precursor films.

Thickness-Dependent Photoelectrochemical Water Splitting Properties of Self-Assembled Nanostructured LaFeO3 Perovskite Thin Films.

Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO3 (LFO) epitaxial thin films as a function of layer’s thickness. The variation with the film’s thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation—<100>SrTiO3//<001> LFO, <100>SrTiO3//<110> LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film’s thicknesses higher than 14 nm, is presented. LFO thin films exhibit different epitaxial orientations depending on their thickness, and the appearance of self-assembled nanopyramids-like domains after a thickness threshold value has proven to have a detrimental effect on the PEC functional properties. Using Nb:SrTiO3 as conductive substrate and 0.5 M NaOH aqueous solution for PEC measurements, the dependence of the photocurrent density and the onset potential vs. RHE on the structural and stoichiometric features exhibited by the LFO photoelectrodes are unveiled by the X-ray diffraction, high-resolution transmission electron microscopy, ellipsometry, and Rutherford backscattering spectroscopy results. The potentiodynamic PEC analysis has revealed the highest photocurrent density Jphotocurrent values (up to 1.2 mA/cm2) with excellent stability over time, for the thinnest LFO/Nb:SrTiO3 sample, both cathodic and anodic behavior being noticed. Noticeably, the LFO thin film shows unbiased hydrogen evolution from water, as determined by gas chromatography in aqueous 0.5 M NaOH solution under constant illumination.

Ion beam induced modification and nanostructures formation in thin SiC/Pd films on c-Si substrate

Ion beam induced modification of thin metallic films is an emerging approach to grow metallic nanoparticles controllably. Modification of thin solid films is helpful in fabricating arrays of nanoscale particles for electronic and photonic devices and for the catalyzed synthesis of nanotubes and nanowires. In this work, the modification and nanostructures formation over the surface of SiC/Pd thin films of 15 and 45 nm thicknesses, grown on crystalline Silicon (c-Si) substrate by electron beam deposition, upon ion irradiation, have been investigated by means of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Rutherford backscattering spectrometry (RBS), Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopy. The SiC/Pd bilayer films were irradiated with 100 keV Ar+ ions at fluences of 1 × 1015 and 5 × 1015 ions/cm2 at room temperature. The surface morphology from SEM analysis showed the formation of nanoparticles that were interconnected after irradiation. The RBS and EDS results confirmed the presence of Pd, C, O and Si. While the Raman spectrum of the pristine sample displayed only a sharp peak at 520 cm−1 characteristic to c-Si substrate, the spectra of the irradiated sample red-shifted to lower wavenumbers indicating the appearance of Si nanocrystals.. Hence, ion beam irradiation is a promising method for the fabrication of SiC nanostructures on c-Si substrate.

Initiation and Polymer Density of Conjugated Polymer Brushes.

The growth mechanism and polymer density in conjugated polymer brush (CPB) films composed of poly(3-methylthiophene) (P3MT) are characterized. X-ray photoelectron spectroscopy experiments show that the initiation of aryl halide monolayers by Pd(PtBu3)2 produces disproportionated monolayer initiators. Unlike disproportionated species formed during the solution-phase initiation of aryl halides, which cannot mediate polymerization, the surface-bound initiators catalyze polymerization to form CPB films with a high grafting density (1.2 nm-2). Rutherford backscattering spectrometry (RBS) experiments show that P3MT CPB films have a characteristic monomer volume density (3.7 nm-3) that is indistinguishable from the volume density of spuncast poly(3-hexylthiophene) films. Using these RBS and XPS results, characteristics of P3MT CPB growth are obtained, including the turnover frequency (7.5 h-1) and polymer molecular weight (300 g/mol·nm).

Effect of rapid thermal annealing on damage of silicon matrix implanted by low-energy rhenium ions

The structural, electronic, and magnetic properties of low-energy rhenium implanted c-Si are examined for the first time. The damage created by rhenium ions and the following partial reconstruction of the silicon host matrix after rapid thermal annealing (RTA) are investigated as a function of the fluence. Rutherford backscattering spectrometry (RBS) results reveal that the implanted ions are located in the near-surface region with the distribution maximum at about 23 nm below the surface. The analysis of rhenium-depth distribution using the McChasy code shows that the implanted Re-ions are located in the interstitial lattice positions. The RTA leads to a partial recovery of the silicon crystal structure. According to the RBS results, the formed inclusions are not coherent with the silicon host matrix causing an increase of the lattice distortion. Analysis of channeled RBS/c spectra carried out by the McChasy code revealed different levels of bent channels in damaged regions suggesting bimodal distribution of inclusions in the silicon. Studies of high-resolution X-ray photoelectron spectroscopy (XPS) conducted after the RTA showed the shift of Re 4f7/2 binding energy (BE) by +0.68 and + 0.85 eV with respect to metallic rhenium for the samples with lower/higher fluencies, respectively. Complex XPS, density functional theory (DFT) simulations, and transmission electron microscopy (TEM) data analysis allowed us to conclude that the near-surface layer of the sample (∼10 nm) consists of nanoinclusions with cubic and/or hexagonal ReSi. In the middle area of the samples, much larger nanoinclusions (>10/20 nm for higher/lower fluencies, respectively) containing pure metallic rhenium inside are formed. The RTA increases the magnetic moment of the sample with the lower dose nearly 20-fold, whereas in the sample with the higher dose a 3-fold increment is observed only. The magnetic response of the examined systems after the RTA indicates a presence of magnetic interactions between the nanoinclusions resulting in the system exhibiting super-spin glass or super-ferromagnetism.

Alloy formation at the Fe-on-Nb and Nb-on-Fe interfaces

Nb/Fe/Nb vacuum evaporated trilayers were studies by X-ray reflectometry, Rutherford backscattering spectrometry and Mössbauer spectroscopy in order to obtain information on the properties of the Fe-on-Nb and Nb-on-Fe interfaces. According to the Mössbauer analysis the interfaces are rather sharp; chemical mixing forms less than 1 nm thick Fe-rich interfaces at both sides of the Fe layer. Comparison to X-ray reflectometry and Rutherford backscattering spectrometry results indicate that interface alloying and geometrical roughness equally contribute to the element distribution across the Fe and Nb layers.

A comparative study of epitaxial InGaAsBi/InP structures using Rutherford backscattering spectrometry, X-ray diffraction and photoluminescence techniques

In this work, we used a combination of photoluminescence (PL), high resolution X-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) techniques to investigate material quality and structural properties of MBE-grown InGaAsBi samples (with and without an InGaAs cap layer) with targeted bismuth composition in the 3%–4% range. XRD data showed that the InGaAsBi layers are more homogeneous in the uncapped samples. For the capped samples, the growth of the InGaAs capped layer at higher temperature affects the quality of the InGaAsBi layer and bismuth distribution in the growth direction. Low-temperature PL exhibited multiple emission peaks; the peak energies, widths, and relative intensities were used for comparative analysis of the data in line with the XRD and RBS results. RBS data at a random orientation together with channeled measurements allowed both an estimation of the bismuth composition and analysis of the structural properties. The RBS channeling showed evidence of higher strain due to possible antisite defects in the capped samples grown at a higher temperature. It is also suggested that the growth of the capped layer at high temperature causes deterioration of the bismuth-layer quality. The RBS analysis demonstrated evidence of a reduction of homogeneity of uncapped InGaAsBi layers with increasing bismuth concentration. The uncapped higher bismuth concentration sample showed less defined channeling dips suggesting poorer crystal quality and clustering of bismuth on the sample surface.

Ion-implanted silver nanoparticles for metal-enhanced fluorescence

Metal Enhanced Fluorescence (MEF) has promising applications in the field of optical displays, bio-sensing and photodynamic therapy. In this work, we exploit the plasmons of embedded silver nanoparticles (Ag NPs) fabricated by ion implantation to enhance the fluorescence of Coumarin515 dye (C515) via MEF. Ion Implantation of 70 keV Ag ions in quartz matrix at different fluences was carried out to synthesize Ag nanoparticles inside quartz matrix. The formation of Ag NPs is characterized by the optical absorption measurements and approximate sizes of Ag NPs was obtained from the fitting of the optical absorption spectra with Mie theory calculations. Rutherford Backscattering Spectrometry (RBS) measurement was used to obtain the depth profile and concentration Ag within the substrate. From the RBS results, it was determined that front edge of the layer containing Ag was formed at an average depth of 16 nm below the surface, which closely agreed with Stopping and Range of Ions in Matter (SRIM) calculations. Increase in the size of the NPs is observed as the fluence of the Ag within the substrate is increased. The MEF of drop casted C515 dye was studied using steady-state emission and excitation spectra measurements. Fluorescence enhancement factor ranging from 1.0 to 2.1 with a maximum enhancement for the largest size NP was obtained. The observed MEF was ascribed to a combination of plasmon enhancement with larger nanoparticles and to increased plasmonic hot spots.

Characterization of compositional modifications in metal-organic frameworks using carbon and alpha particle microbeams

Zirconium-oxide based metal-organic frameworks (MOFs) were grown on p-type Si wafers. A modified linker molecule containing iodine was introduced by post synthetic exchange (PSE). Samples have been studied using Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) techniques, employing the 5MV 15SDH-2 Pelletron Tandem accelerator at the Ångström laboratory. The degree of post synthetic uptake of the iodine-containing linker has been investigated with both a broad beam and a focused beam of carbon and alpha particles targeting different kind of MOF crystals which were of ∼1–10μm in size, depending on the linker used. Iodine concentrations in MOF crystallites were also measured by Nuclear Magnetic Resonance Spectroscopy (NMR) and are compared to the RBS results. In parallel to the ion beam studies, samples were investigated by Scanning Electron Microscopy (SEM) to quantify possible crystallite clustering, develop optimum sample preparation routines and to characterize the potential ion beam induced sample damage and its dependence on different parameters. Based on these results the reliability and accuracy of ion beam data is assessed.

Temperature-Dependent Helium Ion-Beam Mixing in an Amorphous SiOC/Crystalline Fe Composite

Temperature dependent He-irradiation-induced ion-beam mixing between amorphous silicon oxycarbide (SiOC) and crystalline Fe was examined with a transmission electron microscope (TEM) and via Rutherford backscattering spectrometry (RBS). The Fe marker layer (7.2 ± 0.8 nm) was placed in between two amorphous SiOC layers (200 nm). The amount of ion-beam mixing after 298, 473, 673, 873, and 1073 K irradiation was investigated. Both TEM and RBS results showed no ion-beam mixing between Fe and SiOC after 473 and 673 K irradiation and a very trivial amount of ion-beam mixing (~2 nm) after 298 K irradiation. At irradiation temperatures higher than 873 K, the Fe marker layer broke down and RBS could no longer be used to quantitatively examine the amount of ion mixing. The results indicate that the Fe/SiOC nanocomposite is thermally stable and tends to demix in the temperature range from 473 to 673 K. For application of this composite structure at temperatures of 873 K or higher, layer stability is a key consideration.

Sub-monolayer growth of Ag on flat and nanorippled SiO2 surfaces

In-situ Rutherford Backscattering Spectrometry (RBS) and Molecular Dynamics (MD) simulations have been used to investigate the growth dynamics of silver on a flat and the rippled silica surface. The calculated sticking coefficient of silver over a range of incidence angles shows a similar behaviour to the experimental results for an average surface binding energy of a silver adatom of 0.2 eV. This value was used to parameterise the MD model of the cumulative deposition of silver in order to understand the growth mechanisms. Both the model and the RBS results show marginal difference between the atomic concentration of silver on the flat and the rippled silica surface, for the same growth conditions. For oblique incidence, cluster growth occurs mainly on the leading edge of the rippled structure.

The effect of thermal annealing in a hydrogen atmosphere on tungsten deposited on 6H[sbnd]SiC

Tungsten (W) film was deposited on a bulk single crystalline 6HSiC substrate and annealed in H2 ambient at temperatures of 700 °C, 800 °C and 1000 °C for 1 h. The resulting solid-state reactions, phase composition and surface morphology were investigated by Rutherford backscattering spectrometry (RBS), grazing incidence X-ray diffraction (GIXRD) and scanning electron microscopy (SEM) analysis techniques. These results are compared with the vacuum annealed results reported in our earlier work. As-deposited RBS results indicated the presence of W and O2 in the deposited thin film, the GIXRD showed the presence of W, WO3, W5Si3 and WC. RBS results indicated the interaction between W and SiC was accompanied by the removal of oxygen at 700 °C. The GIXRD analysis indicated the presence of W5Si3 and WC in the samples annealed at 700 °C. At temperatures of 800 °C and 1000 °C, W annealed in a H2 ambient further reacted with the SiC substrate and formed a mixed layer containing silicide phases and carbide phases, i.e.W5Si3, WSi2, WC and W2C. The SEM micrographs of the as-deposited samples indicated the W thin film had a uniform surface with small grains. Annealing at 800 °C led to the agglomeration of W grains into clusters making the surface rough.

Interfacial reactions and surface analysis of W thin film on 6H-SiC

Tungsten (W) thin film was deposited on bulk single crystalline 6H-SiC substrate and annealed in vacuum at temperatures ranging from 700 to 1000°C for 1h. The resulting solid-state reactions, phase composition and surface morphology were investigated by Rutherford backscattering spectroscopy (RBS), grazing incidence X-ray diffraction (GIXRD) and scanning electron microscopy (SEM). XRD was used to identify the phases present and to confirm the RBS results. The RBS spectra were simulated using the RUMP software in order to obtain the deposited layer thickness, composition of reaction zone and detect phase formation at the interface. RBS results showed that interaction between W and SiC started at 850°C. The XRD analysis showed that WC and CW3 were the initial phases formed at 700 and 800°C. The concentration of the phases was however, too low to be detected by RBS analysis. At temperatures of 900 and 1000°C, W reacted with the SiC substrate and formed a mixed layer containing a silicide phase (WSi2) and a carbide phase (W2C). The SEM images of the as-deposited samples showed that the W thin film had a uniform surface with small grains. The W layer became heterogeneous during annealing at higher temperatures as the W granules agglomerated into island clusters at temperatures of 800°C and higher.

Surface and interface modification of Zr/SiC interface by swift heavy ion irradiation

In this study thin Zr films (135nm) were deposited on 6H-SiC substrate at room temperature by sputter deposition. The Zr/SiC couples were irradiated by 167MeV Xe26+ ions at room temperature at fluences of 5.0×1012, 1.0×1013, 5.0×1013, 2.0×1014, 3.1×1014 and 6.3×1014ions/cm2. The samples were analysed before and after irradiation using Rutherford backscattering spectroscopy (RBS), atomic force microscopy (AFM) and secondary electron microscopy (SEM). The surface morphology from SEM analysis revealed a homogeneous Zr surface which did not vary with increasing fluences of irradiation. AFM analysis revealed that the Rrms surface roughness did increase from the as-deposited value of 1.6nm and then decrease at higher SHI irradiation fluences to 1.4nm. RBS results indicate that interface mixing between Zr and SiC interface occurred and varied linearly with irradiation ion fluence. The value obtained for diffusivity of Zr shows that the mixing was due to interdiffusion across the interface during a transient melt phase according to the thermal spike model.

Interfacial Mixing In Te/Bi Thin Film System

MeV Ag ions have been used to study the swift heavy ion (SHI) induced modification in Te/Bi bilayer system. The samples were analysed using Rutherford backscattering spectroscopy (RBS), Atomic force microscopy (AFM) and X-ray diffractometer (XRD). The elemental depth study with RBS results show a strong mixing between the top Te layer and the underlying Bi layer on irradiation. Surface roughness as calculated by AFM is found to increase from 8 to 30 nm on irradiation for the fluence 3x10 13 ions/cm 2 . XRD results confirm the formation of Bi-Te alloy phases on mixing and are expected to be formed due to the interfacial reaction taking place within the molten ion tracks. Ion beam mixing has the potential to induce the formation Bi-Te alloy thin films which are the promising candidate for thermoelectric applications near room temperature. Copyright © 2014 VBRI press.

Composition of PbTe oxides obtained by different methods

The widespread use of PbTe nanocomposites requires knowledge regarding the composition of their grain boundaries. Cathodoluminescence (CL), TOF-SIMS and Rutherford backscattering spectroscopy (RBS) were used to explore the composition of surface layers formed via thermal, electrochemical, and wet chemical oxidation of lead telluride. Surface layers obtained by these methods contained components with different degrees of oxidation. RBS and CL results show that thermal and anodic oxidation produced ternary PbTeO3 and Pb2TeO4 oxides, respectively. For the chemical oxide we observed a substantially lower concentration of oxygen described by PbO1−xTeO2−x, a significant amount of non-oxidized PbTe ions detected by SIMS, and low CL stability under electron beam radiation. Thus, the chemical oxide is likely a mixture of binary suboxides.

Swift heavy-ions induced sputtering in BaF2 thin films

In our present experiment a series of barium fluoride thin films of different thicknesses have been deposited by electron beam evaporation technique at room temperature on silicon substrates. The effect of film thickness on the electronic sputter yield of polycrystalline BaF2 thin films has been reported in the present work. Power law for sputtered species collected on catcher grids has also been reported for film of lowest thickness. Sputtering has been performed by 100MeV Au+28 ions. Atomic force microscopy (AFM) has been done to check the surface morphology of pristine samples. Glancing angle X-ray diffraction (GAXRD) measurements show that the pristine films are polycrystalline in nature and the grain size increases with increase in film thickness. Rutherford backscattering spectrometry (RBS) of pristine as well as irradiated films was done to determine the areal concentration of Ba and F atoms in the films. A reduction in the sputter yield of BaF2 films with the increase in film thickness has been observed from RBS results. The thickness dependence sputtering is explained on the basis of thermal spike and the energy confinement of the ions in the smaller grains. Also transmission electron microscopy (TEM) of the catchers shows a size distribution of sputtered species with values of power law exponent 1/2 and 3/2 for two fluences 5×1011 and 1×1012ions/cm2, respectively.