RBS analyses of xenon-irradiated Ti and TiN films

TiN films of 30–300 nm thickness, deposited onto stainless steel via magnetron sputtering, and 10 μm thick Ti foils were irradiated with 80–360 keV Xe⁺ ions at influences of φ = 10¹⁵–10¹⁷ ions/cm². The Xe content was depth-profiled by means of 900 keV He⁺⁺ Rutherford backscattering. Irradiations of films with a thickness exceeding the ion range (at 80 and 250 keV) led to saturation effects due to sputtering and outdiffusion from the near-surface region. The sputtering yields deduced at low Xe fluences were compared to calculations for mono-elemental and compound sputtering. Surface blistering was observed after 250 keV saturation implantation into Ti. For TiN layers with a thickness comparable to the ion range, precipitation of the mixing gas at the interface was observed which finally led to the destruction of the layers. The dependence of the Xe fraction accumulated in the interface is discussed in terms of thermal-spike calculations.     

PIXE measurements of Kr-sputtered TiN coatings

Titanium nitride films of 30–300 nm thickness deposited via dc magnetron sputtering were irradiated with 150–700 keV Kr ions at fluences up to 2.1 × 10¹⁷ cm⁻². These films were then scanned with a well-collimated 400 keV proton beam and the X-ray yield of Ti was measured both in and outside the Kr beam spot. This procedure results in a precision determination of the average film thickness (± 1% in the case of tens of nm films). The PIXE results are found to be consistent with RBS data of the same specimens. Sputtering yields were determined from the variation of X-ray yields assuming unchanged Ti/N stoichiometry in the implanted area. For thick TiN films (d₀ > 100 nm) the sputtering yields are in good agreement with predictions of the collisional cascade model by Sigmund. In contrast, sputtering of thin layers (d₀ = 30 nm) depended sensitively on the ion energy, being a factor of 2 higher at 150 keV than at 500 keV.     

Xenon-ion-beam modifications of a-SiO2 and Ni/a-SiO2 layers

Modifications of a-SiO₂ films and Ni/a-SiO₂ bilayers by irradiations with 90–350 keV Xe ions have been investigated. The effects of subsequent thermal annealings in vacuum at 298–1173 K have also been studied. The analyses were performed by means of Rutherford Backscattering Spectrometry and surface profilometry. We here report on the results of ion-beam induced surface roughening and sputtering and of the noble-gas collection curves. As to the athermal ion-beam mixing at the Ni/a-SiO₂ interface, a low mixing rate in agreement with the ballistic model was observed. Only little Xe precipitation, which would indicate the presence of end-of-range spikes, occurs at the interface. Most effects were found to strongly depend on the implanted ion fluence.     

Comment on “cross sections for sputtering of p(2 × 2) oxygen on Ni(111) by 5–200 eV Ne”

The structure observed in the 5–200 eV Ne⁺ ion induced sputtering cross sections σ for the p(2 × 2) oxide phase on Ni(111) is interpreted in terms of electronic sputtering. Two qualitative mechanisms are suggested as explanations for the unexplained structure in the σ versus kinetic energy curves, suggesting that the structure represents electronic desorption processes that are superimposed on a smooth momentum sputtering curve.     

Molecular dynamics and Monte-Carlo simulation of sputtering and mixing by ion irradiation

Molecular dynamics (MD) and Monte-Carlo (MC) simulations of low-energy (<500 eV) Ar ion irradiation on Si substrates were performed in order to investigate the mixing and sputtering effects. Both MD and MC simulation show similar results in sputtering yield, depth profile of projectile and mixing of substrate. For these incident energies, the depth of the mixed region is determined by the implant range of incident ions. For example, when the incident energy is 500 eV, the Ar ions reach a depth of 40 Å so that the Si atoms that reside shallower than 40 Å are fully mixed at an ion dose of about 5.0×10¹⁶ atoms/cm². The resolution of secondary ion mass spectrometry (SIMS) was also studied. It was found that the resolution of SIMS depends on the depth of mixing, which depends in turn on the implant range of the probe ions. This is because the mixing of substrate atoms occurs more frequently than sputtering, so that the information about the depth profile in the mixing region is disturbed.     

磁控溅射制备金属铀膜

研究了通过磁控溅射方法制备高纯金属铀膜的可行性。采用X射线衍射（XRD）、俄歇电子能谱（AES）、扫描电镜（SEM）、表面轮廓仪分析了沉积在单晶硅或金基材上铀薄膜的微观结构、成分、界面结构及厚度、表面形貌和表面粗糙度。分析结果表明：磁控溅射制备的铀薄膜为纯金属态,氧含量和其它杂质含量均低于俄歇电子能谱仪的探测下限;溅射沉积的铀镀层与铝镀层之间存在界面作用,两者相互扩散并形成合金相,扩散层厚度约为10nm。铀薄膜厚度可达微米级,表面光洁,均方根（RMS）粗糙度优于15nm。     

The development of porosity in thick zirconia films

The pore structures of posttransition oxide films on specimens of Zircaloy-4 fuel cladding oxidised in 340–360°C (613–633 K) water or 400°C (673 K), 10 MPa steam, have been examined by impedance spectroscopy, scanning electron microscopy, and replica transmission electron microscopy of the oxide surfaces, the oxide-metal interfaces (after dissolution of the metal) and fractured oxide cross sections. The results were compared with measurements of the total oxide thickness derived from weight gains, FTIR interferometry, impedance measurements with mercury contacts, and metallographic sections. The various measurements of total thickness were in good general agreement. Impedance measurements during soaking with aqueous ammonium nitrate solution showed two characteristically different types of behaviour, while the impedance spectra of the soaked oxides also showed a dichotomy of behaviour, but for different groups of specimens. The impedance spectra showed surprising similarities for specimens from similar cladding batches but with very different oxide thickness and morphologies, suggesting that micrometallurgical differences between batches may influence oxide structure irrespective of formation conditions and final thickness. Electron microscopy showed relatively few cracks and pores in the outer oxide films formed on belt-ground surfaces, except for the thick white oxide patches formed in 400°C steam. Much higher pore densities were seen at the oxide-metal interface than at the surface, in agreement with the higher volume fraction of t-ZrO₂ expected at the oxide-metal interface. Relative pore densities at the oxide-metal interface correlated well with the relative oxidation rates during the final oxidation period.     

Interface mixing induced by swift heavy ions at metal-oxide/silicon interfaces

It was observed previously that ceramic/ceramic bilayers were very sensitive with respect to the electronic stopping power S_e, i.e. strong interface mixing, scaling with , occurred if a threshold S_ec was exceeded. The threshold seemed to be determined by the higher track formation threshold of two constituents forming the bilayer. Although no track formation has been observed in crystalline Si even for Uranium projectiles, interface mixing was observed previously for some Si-multilayers.

In this paper we report on the interface mixing of NiO, Fe₂O₃, TiO₂ on Si due to irradiation with 90–350 MeV Ar-, Kr-, Xe- and Au-ions at 80 K at fluences up to 9E15 ions/cm². Interface mixing, analyzed by means of Rutherford Backscattering Spectrometry (RBS), is found for these bilayers, too. But the threshold for intermixing is significantly higher compared to the ceramic/ceramic bilayers. This observation could be an evidence for the threshold being determined by the Si-layer. In contrast to NiO/Si and Fe₂O₃/Si, where an usual random walk mixing Δσ² = kΦ was observed, the interface broadening Δσ² for TiO₂/Si is found to scale nonlinearly with the ion fluence, which indicates that mixing is driven by a chemical solid-state reaction. At higher fluences plateaus form at the low energy Ni-edge of the RBS spectra. The plateaus indicate phase formation. X-Ray diffraction spectra does not show any evidence for new crystalline phases.     

Effect of different ion beam energy on properties of amorphous carbon film fabricated by ion beam sputtering deposition (IBSD)

Amorphous carbon (a-C) films were fabricated by ion beam sputtering technique. The influence of sputtering ion beam energy on bonding structure, morphologic, mechanical properties, tribological properties and corrosion resistance of a-C films are investigated systematically. Morphology study shows that lowest surface roughness exists for mid-ion beam energy. Improved adhesion is observed for the films that are prepared under high ion beam energy, attributed to film graphitization, low residual stress and mixed interface. Relatively, a-C films prepared with ion beam energy of 2 keV exhibits optimum sp³ bond content, mechanical properties and corrosion resistance. It is found that the wear rate of DLC films decrease with increased ion beam energy in general, consistent with the varied trend of the H/E value which has been regarded as a suitable parameter for predicting wear resistance of the coatings. The correlation of the sp³ bond fraction in the films estimated from Raman spectroscopy with residual stress, nanohardness and corrosion resistance has been established.     

Metastable phases in Co–Ag system formed by ion beam assisted deposition at the glancing ion incidence

Co metastable structures are formed in Co–Ag alloy films with the aid of glancing incident ions during deposition. The structures of Co are characterized by X-ray absorption near-edge structure (XANES) spectroscopy at the Co K-edge. The results indicate that two kinds of Co phases coexist in every film. One is -Co or β-Co and the other is named fcc-II with a = 4.06 Å. It is thought that the stress between Co and Ag clusters induces the formation of β-Co and the fcc-II phase. The role of glancing incident ions is to trigger a collision cascade on the surface and to facilitate both thermodynamics and kinetics aspects of cluster mixing.     

Sputtering of hydrocarbons by ion-induced breaking of chemical bonds

While the physical sputtering of atoms caused by keV and MeV ions has been studied extensively both by molecular dynamics (MD) simulation and experiments, the mechanisms leading to atom and molecule erosion at energies 1–100 eV are not very well understood. We now describe how low-energy hydrogen ions can cause erosion of carbon atoms and hydrocarbon molecules by entering the region of a carbon–carbon chemical bond and hence breaking it, a process we call ‘swift chemical sputtering'. In the particular case of hydrogen bombardment of carbon-based materials, we further show that this can lead to erosion yields far exceeding those expected for a physical sputtering process.     

Studies of electronic sputtering of fullerene under swift heavy ion impact

The present work reports the dependence of electronic sputtering on thickness of fullerene film. The energetic ions of 200 MeV Au¹⁵⁺ are taken from NSC Pelletron at New Delhi and the Tandem accelerator at Munich. On-line elastic recoil detection analysis (ERDA) with ΔE–E telescope detector is used to determine the electronic sputtering yield. We observed systematic decrease in sputtering yield of carbon with increase in film (C₆₀/silicon) thickness.     

Argon irradiation damage at a Cu/Al2O3 interface for different alumina structures

The evolution of damages at a Cu/Al₂O₃ device interface after Ar⁺ irradiation, depending on alumina structure, and the effect of surface roughness on sputtering have been studied. A polycrystalline Cu/Al₂O₃ bilayer and polycrystalline Cu on amorphous alumina were irradiated with 400 keV Ar⁺ ion beam at doses ranging from 5 × 10¹⁶ to 10¹⁷ Ar⁺/cm² at room temperature. The copper layer thicknesses were between 100 and 200 nm. RBS analysis was used to characterize the interface modification and to deduce the sputtering yield of copper. The SEM technique was used to control the surface topography. A RBS computer simulation program was used to reproduce experimental spectra and to follow the concentration profile evolutions of different elements before and after ion irradiation. A modified TRIM calculation program which takes into account the sputtering yield evolution as well as the concentration variation versus dose gives a satisfactory reproduction of the experimental argon distribution. The surface roughness effect on sputtering and the alumina structure influence at the interface on mixing mechanisms are discussed.     

Atomic mixing at metal–oxide interfaces by high energy heavy ions

We study the atomic mixing at metal (Bi or Au)/oxide (SiO₂ or Al₂O₃) interfaces under 150–200 MeV heavy ion irradiation. Irradiation-induced interface mixing state is examined by means of Rutherford backscattering spectrometry (RBS). For Bi/Al₂O₃ interfaces, the heavy ion irradiations induce a strong atomic mixing and the amount of the mixing increases with increasing the electronic stopping power for heavy ions. By comparing the results with that for 3 MeV Si ion irradiation, we conclude that the strong atomic mixing observed at Bi/Al₂O₃ interfaces is attributed to the high-density electronic excitation. On the other hand, for other interfaces (Bi/SiO₂, Au/Al₂O₃ and Au/SiO₂), atomic mixing is rarely observed after the irradiation. The dependence of atomic mixing on combinations of irradiating ions and interface-forming materials is discussed.     

Reactive ion etching of PECVD silicon nitride in SF6 plasma

The reactive ion etching of PECVD silicon nitride thin films has been investigated using SF₆ plasma. Effects of variations of process parameters such as pressure (50–350 mTorr), RF power (50–250 W), gas flow rate (3–130 sccm) and additions of O₂ and He (0–50%) in SF₆, on the PECVD silicon nitride etch rate and selectivity to the AZ 1350J photoresist were examined. An etch rate of 1 μm/min has been obtained under the condition of 150 mTorr, 100 W and 60 sccm. Experimental results also indicated a maximum etch rate at approximately 30% O₂ while addition of He showed only dilution effect. A nitride/photoresist selectivity ranging from 1 to 3:1 has been obtained.     

Mathematical modeling for the composition prediction of compound films grown by ion-assisted deposition technique and its application to TiNx film

A simple general model has been formulated to explain the composition of compound films during growth simultaneous with ion bombardment. The variables in this model are (a) the sticking probability of the background residual reactive gas in the film, (b) an ion-enhanced sticking probability of these reactive gases arising from ion-enhanced adsorption and mixing and (c) ion implantation of the energetic ions impinging on the growing film. Preferential sputtering of various components in the film is also taken into account. The model is shown to be successful in explaining the experimental variations in the composition of TiN_x films produced by ion-assisted growth.     

H+辐照对不锈钢基体上涂覆W膜的微观研究

对奥氏体不锈钢基体上采用离子束混合技术进行不同厚度的钨膜沉积，沉积后的试样进行了H^ 注入前后的XRD和SEM微观分析，研究了H^ 辐照对W膜的晶体结构和形象的影响。结果表明，沉积的W膜基本上是非晶的，还出现了由于污染造成的钨的氧化物。氢离子的辐照模拟结果表明，少量晶化的W向非晶化转变，污染的氧化物被择优溅射掉。H^ 轰击对W膜表面形貌的影响不大，它仍然致密、均匀、完整且无明显损伤。     

Reactive DC Magnetron Sputter Deposited Titanium-Copper-Nitrogen Nano-Composite Thin Films with an Argon/Nitrogen Gas Mixture

A sintered Ti13Cu87 target was sputtered by reactive direct current (DC) magnetron sputtering with a gas mixture of argon/nitrogen for different sputtering powers. Titanium-copper-nitrogen thin films were deposited on Si (111), glass slide and potassium bromide (KBr) substrates. Phase analysis and structural properties of titanium-copper-nitrogen thin films were studied by X-ray diffraction (XRD). The chemical bonding was characterized by Fourier transform infrared (FTIR) spectroscopy. The results from XRD show that the observed phases are nano-crystallite cubic anti rhenium oxide (anti ReO3) structures of titanium doped Cu3N (Ti:Cu3N) and nano-crystallite face centered cubic (fcc) structures of copper. Scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM/EDX) were used to determine the film morphology and atomic titanium/copper ratio, respectively. The films possess continuous and agglomerated structure with an atomic titanium/copper ratio ( 0.07) below that of the original target ( 0.15). The transmittance spectra of the composite films were measured in the range of 360 to 1100 nm. Film thickness, refractive index and extinction coefficient were extracted from the measured transmittance using a reverse engineering method. In the visible range, the higher absorption coefficient of the films prepared at lower sputtering power indicates more nitrification in comparison to those prepared at higher sputtering power. This is consistent with the formation of larger Ti:Cu3N crystallites at lower sputtering power. The deposition rate vs. sputtering power shows an abrupt transition from metallic mode to poisoned mode. A complicated behavior of the films’ resistivity upon sputtering power is shown.     

Ion energy dependence of interface parameters of ion beam sputter deposited W/Si interfaces

W thin films and W/Si/W tri-layer samples have been deposited on c-Si substrates in a home-made ion beam sputtering system at 1.5 × 10⁻³ Torr Ar working pressure, 10 mA grid current and at different Ar⁺ ion energies between 600 and 1200 eV. Grazing incidence X-ray reflectivity (GIXR) measurements in specular and diffused (detector scan) geometry have been carried out on the above samples. The measured GIXR spectra were fitted with theoretically simulated spectra and the different interface parameters viz., interface width, interface roughness and interface diffusion have been estimated for both Si-on-W and W-on-Si interfaces in the above samples. The variation of the above interface parameters as a function of ion energy used for W sputtering has been studied.     

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.