HRBS/channeling studies of ultra-thin ITO films on Si

High-resolution Rutherford backscattering spectroscopy (HRBS)/channeling techniques have been utilized for a detailed characterization of ultra-thin indium tin oxide (ITO) films and to probe the nature of the interface between the ITO film and the Si(0 0 1) substrate. Channeling studies provide a direct measure of the lattice strain distribution in the crystalline Si substrate in the case of amorphous over layers. The measurements on DC magnetron sputtered ITO films have been carried out using the recently installed HRBS facility at the Centre for Ion Beam Applications (CIBA). The thickness of the ultra-thin (∼9.8 nm) ITO films was calculated from the HRBS spectra having an energy resolution of about 1.4 keV at the superimposed leading (In + Sn) edge of the ITO film. The films were near stoichiometric and the interface between ITO film and Si was found to include a thin SiO_x transition layer. The backscattering yields from (In + Sn) of ITO were equal in random and channeling directions, thereby revealing the non-crystalline nature of the film. Angular scans of HRBS spectra around the off-normal [1 1 1] axis clearly showed a shift in the channeling minimum indicative of compressive strain of the Si lattice at the SiO_x/Si interface. The observed strain was about 0.8% near the interface and decreased to values below our detection limits at a depth of ∼3 nm from the SiO_x/Si interface.     

Studies of effect of deposition parameters on the ZnO films prepared by PLD

Thin films of zinc oxide (ZnO), having different thicknesses were prepared by pulsed laser deposition (PLD) technique onto silicon Si(1 1 1) and quartz (SiO₂) substrates at different partial pressures of oxygen. Rutherford back scattering (RBS) analysis was carried out in order to investigate effect of deposition parameters on thickness of films. Quality of the films was investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses. The thickness of the film was found to increase with oxygen partial pressure for both Si and SiO₂ substrates.     

Interface strain study of thin Lu2O3/Si using HRBS

The interface of thin Lu₂O₃ on silicon has been studied using high-resolution RBS (HRBS) for samples annealed at different temperatures. Thin rare earth metal oxides are of interest as candidates for next generation transistor gate dielectrics, due to their high-k values allowing for equivalent oxide thickness (EOT) of less than 1 nm. Among them, Lu₂O₃ has been found to have the highest lattice energy and largest band gap, making it a good candidate for an alternative high-k gate dielectric. HRBS depth profiling results have shown the existence of a thin (∼2 nm) transitional silicate layer beneath the Lu₂O₃ films. The thicknesses of the Lu₂O₃ films were found to be ∼8 nm and the films were determined to be non-crystalline. Angular scans were performed across the [1 1 0] and [1 1 1] axis along planar channels, and clear shifts in the channeling minimum indicate the presence of Si lattice strain at the silicate/Si interface.     

Structural analysis of DC magnetron sputtered and spin coated thin films using RBS, TEM and X-ray reflectivity methods

Metallic thin films such as Au, Cr, Ag, etc., on silicon substrate have many technologically important applications as contact layers in microelectronic industry, as reflecting mirrors in synchrotron radiation research, etc. The native oxide layer on crystalline silicon surface inhibits wetting of few nm thick Au or Ag on native oxide/silicon systems. To obtain continuous thin metallic films (a few nm thick), a Cr layer was first deposited as a adhesion layer on the Si substrate. In this paper, Rutherford backscattering analysis (RBS) of Si/Cr/SiO₂/Si, Si/Au/SiO₂/Si, Si/Au/Cr/SiO₂/Si and Polystyrene (PS) polymer coated on some of these bi- or tri-layer structures has been reported. The X-ray reflectometry and transmission electron microscopy studies were carried out to complement the RBS measurements. The thickness, surface and interface roughness, and crystalline quality have been determined.     

Effects of MeV Si ions bombardment on the thermoelectric generator from SiO2/SiO2 + Cu and SiO2/SiO2 + Au nanolayered multilayer films

The defects and disorder in the thin films caused by MeV ions bombardment and the grain boundaries of these nanoscale clusters increase phonon scattering and increase the chance of an inelastic interaction and phonon annihilation. We prepared the thermoelectric generator devices from 100 alternating layers of SiO₂/SiO₂ + Cu multi-nano layered superlattice films at the total thickness of 382 nm and 50 alternating layers of SiO₂/SiO₂ + Au multi-nano layered superlattice films at the total thickness of 147 nm using the physical vapor deposition (PVD). Rutherford Backscattering Spectrometry (RBS) and RUMP simulation have been used to determine the stoichiometry of the elements of SiO₂, Cu and Au in the multilayer films and the thickness of the grown multi-layer films. The 5 MeV Si ions bombardments have been performed using the AAMU-Center for Irradiation of Materials (CIM) Pelletron ion beam accelerator to make quantum (nano) dots and/or quantum (quantum) clusters in the multilayered superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after Si ion bombardments we have measured Seebeck coefficient, cross-plane electrical conductivity, and thermal conductivity in the cross-plane geometry for different fluences.     

Effects of composition and structure on hydrogen incorporation in tungsten oxide films deposited by sputtering

The effects of composition and structure on hydrogen incorporation in tungsten oxide films were investigated. Films were deposited on carbon and SiO₂ substrates using a reactive sputtering by varying the substrate temperature from 30 to 600 °C in argon and oxygen mixture. The films were characterized using X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), elastic recoil detection analysis (ERDA) and Raman scattering. XRD patterns showed amorphous structure in the films deposited below 400 °C and (0 1 0) oriented monoclinic WO₃ in the films deposited beyond 400 °C. The results of RBS and ERDA indicated that hydrogen concentration in the amorphous films increased from 0.1 to 0.7 H/W with changing the composition from WO_0.25 to WO₃. The hydrogen concentration in WO₃ films decreased to 0.4 H/W with increasing the substrate temperature during deposition. The Raman spectra of the WO₃ films revealed that decreasing of W⁶⁺O terminals was related to decreasing of the hydrogen concentration. It was considered that the incorporated hydrogen in tungsten oxide films was bonded at the end of W⁶⁺O terminals.     

Photoluminescence and radiation effect of Er and Pr implanted silicon-rich silicon oxide thin films

Er and Pr ions were implanted into silicon-rich silicon oxide (SRSO) thin films with Si crystals embedded in SiO₂ matrix. The 525 and 546 nm luminescence peaks were clearly observed in Er-only doped film, but disappeared in the photoluminescence (PL) spectra of Er-Pr codoped films. Instead, a broad PL spectrum extending from 450 to 700 nm was obtained for Er-Pr codoped films with Er/Pr concentration ratio of 1. Concentration profiles of Si, Er and Pr ions in films were simulated by SRIM2006 and related radiation effect on PL response was also discussed. Our results indicate that this material is a potential candidate for the development of white light-emitting diode (LED) and field emission displays for its visible luminescence.     

Nanoscale characterisation of ODS-Eurofer 97 steel: An atom-probe tomography study

Laser-pulsed atom-probe tomography has been used to study the nanoscale features present in an ODS-Eurofer 97 alloy. A core/shell structure was found for particles 5-10 nm in diameter. The particle cores were primarily Y and O, enriched with Mn and Si resulting in a metal (Y, Mn and Si) to oxygen ratio of M:O ∼2:3. The ∼2 nm thick outer-shell region of the particles exhibited partitioning of V, Cr, Ta, C and N together with the core elements in many cases. Detailed compositional measurements have also been made on the smallest of the yttria-based oxide clusters down to 2 nm in diameter. The 2 nm clusters were found to have a non-stoichiometric oxide composition, enriched in oxygen compared to Y₂O₃, and evidence for the existence of a shell around these smaller particles was found.     

Compositional analysis of atom beam co-sputtered metal-silica nanocomposites by Rutherford backscattering spectrometry

Metal:SiO₂ (metal: Ni, Ag, Au) nanocomposite films of different compositions have been prepared by atom beam co-sputtering. The estimation of composition of films is done theoretically using sputtering yield and relative area of metal and SiO₂. The sputtering yields used for estimation of composition are calculated by three theoretical methods: Monte Carlo simulations (SRIM code), Sigmund’s theory and Sigmund’s theory modified by Anderson and Bay. Rutherford backscattering spectrometry (RBS) is also used to analyze the composition of the nanocomposite films. RUMP simulations of RBS data are performed. The errors in theoretical calculations and RBS results are estimated. It is found that SRIM is more appropriate for Ni:SiO₂ nanocomposite films, while modified Sigmund’s theory based method is better for Ag:SiO₂ and Au:SiO₂ nanocomposite films. The possible sources of errors in theoretical methods with respect to experimental (RBS) results are also discussed.     

MeV-ion beam analysis of the interface between filtered cathodic arc-deposited a-carbon and single crystalline silicon

Amorphous carbon (a-C) films were deposited on Si(1 0 0) wafers by a filtered cathodic vacuum arc (FCVA) plasma source. A negative electrical bias was applied to the silicon substrate in order to control the incident energy of carbon ions. Effects of the electrical bias on the a-C/Si interface characteristics were investigated by using standard Rutherford backscattering spectrometry (RBS) in the channeling mode with 2.1-MeV He²⁺ ions. The shape of the Si surface peaks of the RBS/channeling spectra reflects the degree of interface disorder due to atomic displacement from the bulk position of the Si crystal. Details of the analysis method developed are described. It was found that the width of the a-C/Si interface increases linearly with the substrate bias voltage but not the thickness of the a-C film.     

Positron annihilation on the surfaces of SiO2 films thermally grown on single crystal of Cz-Si

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO₂, SiO₂ films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10⁻³m₀c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO₂ and Si without oxide film. However, for the thermally grown SiO₂-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO₂-Si system consist of a surface layer, a SiO₂ layer, a SiO₂-Si interface layer and a semi-infinite Si substrate.     

Spectral analysis method for deriving RBS-like carbon spectra from the C(α,α)C resonant reaction

This article presents a spectral analysis method that detects C using the high-sensitivity of the 4.26 MeV resonance of the ¹²C(α,α)¹²C nuclear reaction while avoiding issues arising from the peaky and asymmetric resonance shape, which complicates depth-sensitive C analysis. By averaging nuclear reaction spectra taken with a set of conveniently chosen He beam energies, we obtain C spectra with amplified intensity, but shape similar to Rutherford backscattering spectrometry (RBS) spectra. The latter fact allows intuitive reading of underlying C depth profiles without employing spectrum simulation software. The method was first applied to simulated samples whose nuclear reaction spectra were generated by SIMNRA, which allowed checking for method accuracy by comparison to corresponding simulated RBS spectra. As real examples of the method application, it was applied to detect depth-sensitive C signals from SiC substrates covered by SiO₂ layers and from 50 nm hafnium-based films deposited on Si by metal-organic chemical vapor deposition.     

Structural characterization of Fe/Ag bilayers by RBS and AFM

Fe/Ag thin films are intensively investigated due to their special magnetic properties. Recently a deposition-order dependent asymmetric interface has been found. When iron is grown on silver, the interface is sharp, while the growth of Ag on Fe results in a long, low-energy tail of the Ag peak in the Rutherford backscattering spectrometry (RBS) spectra. The main purpose of this paper is to show that the low-energy Ag tail is caused by grain boundary diffusion, and that, when elevating the growing temperature of the Ag layer this effect becomes more significant. Two sets of polycrystalline and epitaxial Fe/Ag bilayers were prepared simultaneously onto Si(1 1 1) and MgO(1 0 0), respectively. The iron layers were grown at 250 °C and annealed at 450 °C in both sets, while the Ag layer was grown in the first set at room temperature (RT) and in the second set at 250 °C (HT). The sample composition, the interface sharpness and the quality of the epitaxy were studied by Rutherford backscattering spectrometry (RBS) combined with channeling effect. The surface morphology was determined by atomic force microscopy (AFM). RBS spectra show that in the case of RT samples the epitaxial MgO/Fe/Ag bilayer has sharp, well-defined interface, while for the polycrystalline Si/Fe/Ag sample the silver peak has a low-energy tail. Both the Fe and Ag peaks smeared out in the case of HT samples. AFM-images show that the RT samples have a continuous Ag layer, while the HT samples have fragmented surfaces. The RBS spectra taken on the HT samples were successfully simulated by the RBS-MAST code taking into account their fragmented structures.     

Radiation effect on the photoluminescence properties of Si/SiO2 thin films

Silicon ions were implanted into SiO₂ thin films with various doses and energies. For the films implanted with various ion doses the photoluminescence (PL) intensity of 470 nm firstly increased with the increase of Si ion dose, which is similar to the variation trend of displacement per atom (DPA) number during ion radiation. Further increasing Si ion dose the PL intensity of 470 nm decreased gradually since the neutral oxygen vacancy centers were destroyed. For the samples implanted with different energy the variation trend of PL intensity for 470 nm peak is similar to the result of DPA under different radiation energy according to SRIM2006 simulation. With the increase of radiation energy a new PL peak at 550 nm appeared because of the variation of defect type. Combining with the simulation results and PL spectra the radiation effect on Si/SiO₂ thin films were proposed.     

Hydrogen behavior in gasochromic tungsten oxide films investigated by elastic recoil detection analysis

Changes in the composition and crystalline structure of gasochromic tungsten oxide films resulting from the incorporation of hydrogen were investigated; the oxide films were prepared by reactive RF magnetron sputtering on SiO₂ and glassy carbon substrates simultaneously. X-ray diffraction analysis of the deposited films at 600 °C showed a uniaxial oriented structure in the (0 1 0) plane of monoclinic WO₃ for both substrates. The elastic recoil detection analysis (ERDA) and Rutherford backscattering spectroscopy (RBS) for the films on glassy carbon revealed that the hydrogen impurity was uniformly distributed up to a concentration of 0.24 H/W. The Pd-coated films on SiO₂ turned blue when they were exposed to a mixture of Ar and 5% H₂ gases. When the sample became colored, the hydrogen concentration in the film increased to 0.47 H/W and the crystalline structure of the film changed from monoclinic to tetragonal. These results indicated that the gasochromic coloration of the tungsten oxide films coincided with incorporation of hydrogen atoms into the crystalline lattice, corresponding to the formation of hydrogen tungsten bronze (H_xWO₃).     

Structural and gasochromic properties of epitaxial WO3 films prepared by pulsed laser deposition

The structural and gasochromic properties of epitaxial tungsten trioxide (WO₃) thin films, prepared by ArF excimer pulsed laser deposition under the controlled oxygen atmosphere, have been investigated. The WO₃ films were grown on the α-Al₂O₃ substrates, as the oxygen pressure ranged from 0.57 to 1.20 Pa and the substrate temperature ranged from 432 to 538 °C. The deposited films were characterized by Rutherford backscattering spectroscopy (RBS)/channeling, X-ray diffraction, X-ray pole figures and Raman spectroscopy. RBS and XRD results demonstrated that monoclinic WO₃ (0 0 1) films were successfully grown on the α-Al₂O₃ substrates. The crystal quality was improved by increasing both the oxygen pressure and the substrate temperature. Gasochromic coloration in the WO₃ films by exposure to diluted hydrogen gas was found to correlate with the crystal quality of the films. The gasochromic coloration was suppressed by the epitaxial growth of the films.     

Structural studies of Ge nanocrystals embedded in SiO2 matrix

Germanium nanoparticles embedded in SiO₂ matrix were prepared by atom beam sputtering on a p-type Si substrate. The as-deposited films were annealed at temperatures of 973 and 1073 K under Ar + H₂ atmosphere. The as-deposited and annealed films were characterized by Raman, X-ray diffraction and Fourier transform infrared spectroscopy (FTIR). Rutherford backscattering spectrometry was used to quantify the concentration of Ge in the SiO₂ matrix of the composite thin films. The formation of Ge nanoparticles were observed from the enhanced intensity of the Ge mode in the Raman spectra as a function of annealing, the appearance of Ge(3 1 1) peaks in the X-ray diffraction data and the Ge vibrational mode in the FTIR spectra. We have irradiated the films using 100 MeV Au⁸⁺ ions with a fluence of 1 × 10¹³ ions/cm² and subsequently studied them by Raman and FTIR. The results are compared with the ones obtained by annealing.     

The interdiffusion and solid-state reaction of low-energy copper ions implanted in silicon

At room temperature, single-crystal silicon was implanted with Cu⁺ ions at an energy of 80 keV using two doses of 5 × 10¹⁵ and 1 × 10¹⁷ Cu⁺ cm⁻². The samples were heat treated by conventional thermal annealing at different temperatures: 200 °C, 230 °C, 350 °C, 450 °C and 500 °C. The interdiffusion and solid-state reactions between the as-implanted samples and the as-annealed samples were investigated by means of Rutherford backscattering spectrometry (RBS) and X-ray diffraction (XRD). After annealing at 230 °C, the XRD results of the samples (subject to two different doses) showed formation of Cu₃Si. According to RBS, the interdiffusion between Cu and Si atoms after annealing was very insignificant. The reason may be that the formation of Cu₃Si after annealing at 230 °C suppressed further interdiffusion between Si and Cu atoms.     

Positron annihilation and X-ray diffraction studies on tin oxide thin films

Positron annihilation spectroscopy along with glancing incidence X-ray diffraction have been used to investigate tin oxide thin films grown on Si by pulsed laser deposition. The films were prepared at room temperature and at 670 K under oxygen partial pressure. As-grown samples are amorphous and are found to contain large concentration of open volume sites (vacancy defects). Post-deposition annealing of as-grown samples at 970 K is found to drastically reduce the number of open volume sites and the film becomes crystalline. However, film grown under elevated temperature and under partial pressure of oxygen is found to exhibit a lower S-parameter, indicating lower defect concentration. Based on the analysis of experimental positron annihilation results, the defect-sensitive S-parameter and the overlayer thickness of tin oxide thin films are deduced. S-W correlation plots exhibit distinct positron trapping defect states in three samples.     

Thickness and MeV Si ions bombardment effects on the thermoelectric properties of Ce3Sb10 thin films

The three single layer Ce₃Sb₁₀ thin films were grown on silicon dioxide and quartz (suprasil) substrates with thicknesses of 297, 269 and 70 nm using ion beam assisted deposition (IBAD) technique. The high-energy cross plane Si ion bombardments with constant energy of 5 MeV have been performed with varying fluence from 1 × 10¹², 1 × 10¹³, 1 × 10¹⁴, 1 × 10¹⁵ ions/cm². The Si ions bombardment modified the thermoelectric properties of films as expected. The fluence and temperature dependence of cross plane thermoelectric parameters that are Seebeck coefficient, electrical and thermal conductivities were determined to evaluate the dimensionless figure of merit, ZT. Rutherford backscattering spectrometry (RBS) enabled us to determine the elemental composition of the deposited materials and layer thickness of each film.