Ion beam studies on reactive DC sputtered manganese doped indium tin oxide thin films

Indium based transparent conducting oxides doped with magnetic elements have been studied intensively in recent years with a view to develop novel ferromagnetic semiconductors for spin-based electronics. In the present work, we have grown manganese doped indium tin oxide (Mn:ITO) thin films, onto Si and Si/SiO₂ substrates by DC reactive sputtering of a composite target containing indium-tin alloy and manganese, in a gas mixture of oxygen and argon. Glancing angle X-ray diffraction (GXRD) studies reveal the polycrystalline nature of the films. Magnetic measurements carried out using vibrating sample magnetometer (VSM) suggest that the films are ferromagnetic at room temperature, with a saturation magnetization of ∼22.8 emu/cm³. The atomic percentages of In, Sn, Mn and O, as estimated using Rutherford backscattering spectrometry (RBS) are 37.0, 4.0, 1.6 and 57.4, respectively. RBS measurements reveal that the interface of the films with Si substrate has a ∼30 nm thick intermediate layer. This layer consists of oxygen, silicon, indium, tin and manganese, in the ratio 1:0.56:0.21:0.07:0.03, indicative of diffusion of elements across the interface. The films on Si/SiO₂, on the other hand, have a sharp interface.     

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.     

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.     

Epitaxial 3C-SiC nanocrystal formation at the SiO2/Si interface after carbon implantation and subsequent annealing in CO atmosphere

3C-SiC nanocrystallites were epitaxially formed on a single crystalline Si surface covered by a 150 nm thick SiO₂ capping layer after low dose carbon implantation and subsequent high temperature annealing in CO atmosphere. Carbon implantation is used to introduce nucleation sites by forming silicon–carbon clusters at the SiO₂/Si interface facilitating the growth of 3C-SiC nanocrystallites.     

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.     

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.     

Genesis capturing the sun: Solar wind irradiation at Lagrange 1

Genesis, a member of NASAs Discovery Mission program, is the world’s first sample return mission since the Apollo program to bring home solar matter in ultra-pure materials. Outside the protection of Earth’s magnetosphere at the Earth-Sun Lagrange 1 point, the deployed sample collectors were directly exposed to solar wind irradiation. The natural process of solar wind ion implantation into a highly pure silicon (Si) bulk composition array collector has been measured by spectroscopic ellipsometry and scanning transmission electron microscopy (STEM). Ellipsometry results show that bulk solar wind ions composed of approximately 95% H⁺, 4% He⁺ and <1% other elements physically altered the first 59-63 nm of crystalline silicon substrate during 852.8 days of solar exposure. STEM analysis confirms that the solar accelerated ions caused significant strain and visible structural defects to the silicon structure forming a 60-75 nm thick irradiation damage region directly below the surface SiO₂ native oxide layer. Monte Carlo simulations of solar wind H, He, C, O, Ne, Mg, Si and Fe ion collisions in the Si collector with fluences calculated from the Genesis and ACE spacecrafts were used to estimate the energy deposited and Si vacancies produced by nuclear stopping in a flight-like Si bulk array collector. The coupled deposited energy model with the flown Genesis Si in situ measurements provides new insight into the basic principles of solar wind diffusion and space weathering of materials outside Earth’s magnetosphere.     

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.     

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.     

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.     

High energy Si ions bombardment effects on the properties of nano-layers of SiO2/SiO2 + Ag

We grew 50 periodic SiO₂/SiO₂ + Ag multi-layers by electron beam deposition technique. The co-deposited SiO₂ + Ag layers are 7.26 nm, SiO₂ buffer layers are 4 nm, and total thickness of film was determined as 563 nm. We measured the thickness of the layers using in situ thickness monitoring during deposition, and optical interferometry afterwards. The concentration and distribution of Ag in SiO₂ were determined using Rutherford backscattering spectrometry (RBS). In order to calculate the dimensionless figure of merit, ZT, the electrical conductivity, thermal conductivity and the Seebeck coefficient of the layered structure were measured at room temperature before and after bombardment with 5 MeV Si ions. The energy of the Si ions was chosen such that the ions are stopped deep inside the silicon substrate and only electronic energy due to ionization is deposited in the layered structure. Optical absorption (OA) spectra were taken in the range 200–900 nm to monitor the Ag nanocluster formation in the thin layers.     

Synchrotron X-ray induced damage in polymer (PS) thin films

Thin polystyrene (PS) films (M_w = 234,000) are spin coated on silicon substrates with a Chromium (Cr) layer as a sandwiched metallic layer that produces photoelectrons (by synchrotron X-rays). Earlier studies on synchrotron radiation damage in PS films, without metallic layer, have shown a decrease in interfacial roughness and a slight increase in thickness, at temperatures below T_g [A.G. Richter, R. Guico, K. Shull, J. Wang, Macromolecules 39 (2006) 1545]. Similar trend is observed in the presence of a thin layer of Cr film (∼2.5 nm). For the sample with a thick Cr layer the opposite effect was observed for X-ray radiation damage. For the 50 nm thick Cr film system thickness of the polystyrene film decreased by ≈4.4% which amount to a loss of about 0.021 nm³ per incident photon in the fluence range studied (6.8 × 10⁹ photons mm⁻² to 1 × 10¹⁴ photons mm⁻²). Interfacial roughness also increased from about 1.0 nm to 2.1 nm in the process. These effects are explained by invoking the presence of more number of X-ray induced photoelectrons and secondary electrons for 50 nm thick Cr film case compared to 2.5 nm thin film case.     

Three dimensional measurement of nanostructures by single event TOF-RBS with nuclear nano probe

Single, double and triple-layer test structures were measured by time of flight (TOF) Rutherford backscattering spectrometry (RBS) for checking the sensitivity and resolution. A single-layer nanostructure with Au stripes on a Si substrate was resolved by TOF-RBS measurement within a short time of 256 s. The spatial resolution, measured by the edge of the Au stripes, was 42 nm. Another single-layer nanostructure with Pt stripes fabricated by electron beam (EB) induced deposition on a Si substrate was resolved by TOF-RBS measurement even at a thickness of Pt stripes less than one mono-layer. Ga embedded layers implanted by a focused ion beam under the Pt stripes fabricated by EB induced deposition on a Si substrate could be detected for a double-layer nanostructure. Furthermore, a triple-layer nanostructure with two Pt stripe layers isolated by a SiO₂ layer fabricated by EB induced deposition on a Si substrate could be resolved and cross-sections shown.     

Mechanism of elongation of gold or silver nanoparticles in silica by irradiation with swift heavy ions

It has been reported that elongated Au nanoparticles oriented parallel to one another can be synthesized in SiO₂ by ion irradiation. Our aim was to elucidate the mechanism of this elongation. We prepared Au and Ag nanoparticles with a diameter of 20 nm in an SiO₂ matrix. It was found that Au nanoparticles showed greater elongated with a higher flux of ion beam and with thicker SiO₂ films. In contrast, Ag nanoparticles split into two or more shorter nanorods aligned end to end in the direction parallel to the ion beam. These experimental results are discussed in the framework of a thermal spike model of Au and Ag nanorods embedded in SiO₂. The lattice temperature exceeds the melting temperatures of SiO₂, Au and Ag for 100 ns after one 110 MeV Br¹⁰⁺ ion has passed through the middle of an Au or Ag nanorod.     

Adhesion of proton beam written high aspect ratio hydrogen silsesquioxane (HSQ) nanostructures on different metallic substrates

Hydrogen silsesquioxane (HSQ) behaves as a negative resist under MeV proton beam exposure. HSQ is a high-resolution resist suitable for production of tall (<1.5 μm) high aspect ratio nanostructures with dimensions down to 22 nm. High aspect ratio HSQ structures can be used in many applications, e.g. nanofluidics, biomedical research, etc. Isolated HSQ nanostructures, however, tend to detach from substrates during the development process due to the weak adhesive forces between the resist and the substrate material. Larger proton fluences were observed to promote the adhesion. To determine an optimal substrate material and the proton irradiation doses for HSQ structures, a series of 2 μm long and 60-600 nm wide free-standing lines were written with varying fluences of 2 MeV protons in 1.2 μm thick HSQ resist spun on Ti/Si, Cr/Si and Au/Cr/Si substrates. The results indicate that the Ti/Si substrate is superior in terms of adhesion, while Au/Si is the worst. Cr/Si is not suitable as a substrate for HSQ resist because debris was formed around the structures, presumably due to a chemical reaction between the resist and Cr.     

Nanometer-thick SGOI structures produced by Ge+ ion implantation of SiO2 films and subsequent hydrogen transfer of Si layers

Nanometer-thick silicon-germanium-on-insulator (SGOI) structures have been produced by the implantation of Ge⁺ ions into thermally grown SiO₂ layer and subsequent hydrogen transfer of silicon film on the Ge⁺ ion implanted substrate. The intermediate nanometer-thick Ge layer has been formed as a result of the germanium atom segregation at the Si/SiO₂ bonding interface during annealing at temperatures 800–1100 ^оС. From a thermodynamic analysis of Si/Ge/SiO₂ system, it has been suggested that the growth of the epitaxial Ge layer is provided by the formation of a molten layer at the Si/SiO₂ interface due to the Ge accumulation. The effect of germanium on the hole mobility in modulation-doped heterostructures grown over the 3–20 nm thick SGOI layers was studied. An increase in the Hall hole mobility in SGOI-based structures by a factor of 3–5 was obtained in comparison with that in respective Ge-free SOI structures.     

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).     

Combined grazing incidence RBS and TEM analysis of luminescent nano-SiGe/SiO2 multilayers

Multilayer structures with five periods of amorphous SiGe nanoparticles/SiO₂ layers with different thickness were deposited by Low Pressure Chemical Vapor Deposition and annealed to crystallize the SiGe nanoparticles. The use of grazing incidence RBS was necessary to obtain sufficient depth resolution to separate the signals arising from the individual layers only a few nm thick. The average size and areal density of the embedded SiGe nanoparticles as well as the oxide interlayer thickness were determined from the RBS spectra. Details of eventual composition changes and diffusion processes caused by the annealing processes were also studied. Transmission Electron Microscopy was used to obtain complementary information on the structural parameters of the samples in order to check the information yielded by RBS. The study revealed that annealing at 900 °C for 60 s, enough to crystallize the SiGe nanoparticles, leaves the structure unaltered if the interlayer thickness is around 15 nm or higher.     

离子束辅助沉积(IVD)方法制备Ag/Si薄膜

离子束辅助沉积(以下简称IVD)方法是将离子束技术与真空沉积薄膜技术相结合的一种新的制膜方法。它具有沉积速率高、薄膜吸附强度大、薄膜外延温度低并能消除膜应力等优点。因此,近年来在国际上受到重视和发展。     

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.