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.     

Analysis of annealing and ion implantation effects in Ti/TiN contacts on silicon

The effects of thermal annealing and 350 keV As⁺ ion implantation on interdiffusion processes in a c-Si/Ti/TiN system were analysed. The Ti/TiN contacts were deposited by sputtering (Ti, 100 nm) and by reactive sputtering (TiN, 50 nm) on (111) n-Si wafers. Characterization included RBS, SEM and XRD analysis and electrical measurements. During vacuum annealing, interdiffusion is observed at the Si/Ti interface, where intermixing and growth of silicides takes place at 600° C and at higher temperatures. Annealing in a nitrogen atmosphere induces changes in surface morphology and stoichiometry of TiN, which does not affect the reaction at Si/Ti. Implantation of As⁺ to doses above 3.9 × 10¹⁴ ions/cm² enhances intermixing at the Si/Ti interface during post-implantation annealing, while the TiN overlayer is unaffected in structure and morphology.     

Depth profiling of heavy-ion-mixed TiN films

A survey is given on the modifications of 30–300 nm thin TiN films on various substrates under high-fluence irradiation with 80–700 keV Ar, Kr and Xe ions. In particular, the effects of sputtering, interface mixing and blister formation were investigated. The results were obtained by combining several depth-profiling techniques, such as resonant nuclear reaction analysis (RNRA), Rutherford backscattering spectroscopy (RBS) and proton-induced X-ray emission (PIXE). Scanning electron microscopy and adhesion tests were also applied to the films. Optimal interface mixing parameters are proposed on the basis of the measured sputtering and mixing rates.     

Surface swelling of sapphire induced by MeV and GeV heavy ions

-Al₂O₃ single crystals were bombarded with MeV xenon ions from 10¹⁵ to 10¹⁷ ions cm⁻² and GeV uranium ions from 10¹¹ to 10¹³ ions cm⁻² to study the surface swelling of sapphire at 77 and 300 K due to atomic collision processes (Xe) and electronic energy loss processes in the 20–45 keV/nm regime (U). The induced damage was studied by channeling Rutherford backscattering. Surface swelling was measured with a profilometer. The step height induced by nuclear cascades of MeV xenon increases with the ion fluence and saturates. With GeV uranium, an electronic stopping power threshold for surface swelling was observed and the step height increased with the damage for dE/dx higher than this threshold.     

Sputtering yield and residual vacuum influence during titanium implantation into iron

Ti implantation into iron-based alloys is known to improve tribological properties (low friction and wear) by formation of an amorphous Fe-Ti-C surface layer due to the interaction of the carbonaceous molecules in the residual vacuum with the surface during implantation. To state precisely the conditions of this amorphous-layer formation, thin evaporated iron targets were implanted with 110 keV Ti ions at room temperature with fluences ranging from 6 × 10¹⁶ to 3 × 10¹⁷ Ti/cm² and at different residual pressures. Samples were analysed using backscattering spectrometry with 5.7 MeV ⁴He ions to obtain titanium profiles and to follow the evolution of sputtering yield versus fluence and residual vacuum pressure, and also for determining the amount of carbon and oxygen incorporated on the Ti-implanted surface as a function of fluence and pressure. Theoretical calculations of sputtering and high-fluence Ti distributions were performed and compared to experimental data. The importance of the reactions that occur between the implanted surface and the residual gases in the vacuum during implantation (C and O competition) is discussed.     

Effects of xenon implantation in spinel-zirconia/ceria composites

Two prethinned spinel specimens containing either Y_0.15Zr_0.85O₂ or Ce_0.5Zr_0.5O₂ particles were implanted with 200–400 keV Xe ions at 873 K using the IVEM-Tandem Facility at Argonne National Laboratory. In situ transmission electron microscopy (TEM) was conducted during the implantation in order to follow the evolution of the microstructure. At an ion fluence between 2.4x10²⁰ to 3x10²⁰ m⁻² (up to 50 dpa and 4.7 at %), large Xe bubbles of 50–100 nm developed at the boundaries of the small oxide particles, while a high density of dislocation loops (up to 8 nm in diameter) and much smaller bubbles (up to 4 nm in diameter) formed in the spinel matrix. No large bubbles were observed at the boundaries between the spinel grains. These results suggest that the boundaries between spinel and oxide particles are preferred sites for fission gas accumulation.     

Ion implantation doping and electrical conductivity enhancement of C60 films

Pristine C₆₀ films sublimed onto sheet mica were implanted with 20 keV K⁺ ions and I⁺ ions at doses of 1.0 × 10¹⁶/cm², 3.0 × 10¹⁶/cm² and 5.0 × 10¹⁶/cm², and with 20 keV Ar⁺ ions at a dose of 5.0 × 10¹⁶/cm². The distributions of dopants were studied using Rutherford backscattering spectrometry (RBS). The temperature dependence of sheet resistivity of the films was investigated applying a four-probe system. It was proposed that the conductivity enhancement of K⁺ implanted C₆₀ films was due to the implanted ions in the films, while for I⁺ implanted C₆₀ films, both implanted I⁺ ions and irradiation effects of the ions contributed to the enhancement of conductivity.     

Carbon clustering in Si1−xCx formed by ion implantation

Silicon-carbon alloys were formed by multiple energy implantation of C⁺ ions in silicon and in Silicon on Sapphire (SOS). The ion fluence ranged between 5 × 10¹⁶ − 3 × 10¹⁷ ions/cm² and the energy between 10–30 keV in order to obtain constant carbon concentration into a depth of 100 nm. The carbon atomic fraction (x) was in the range 0.22–0.59 as tested by Rutherford backscattering spectrometry (RBS). Thermal annealing of the implanted films induced a transition from amorphous to a polycrystalline structure at temperatures above 850°C as detected by Infrared spectrometry (IR) in the wavenumber range 600–900 cm⁻¹. The optical energy gap and the intensity of the infrared signal after annealing at 1000°C depended on the film composition: they both increased linearly with carbon concentration reaching a maximum at the stoichiometric composition (x = 0.5). At higher carbon concentration the IR intensity saturated and the optical energy gap decreased from the maximum value of 2.2 to 1.8 eV. The behaviour at the high carbon content has been related to the formation of graphitic clusters as detected by Raman spectroscopy.     

Lattice location and electrical conductivity in ion implanted TiO2 single crystals

Single crystals of TiO₂ (rutile) were implanted at room temperature with Ar, Sn and W ions applying fluences of 10¹⁵/cm² to 10¹⁶/cm² at 300 keV. The lattice location, together with ion range and damage distribution was measured with Rutherford Backscattering and Channeling (RBS-C). The conductivity, σ, was measured as a function of temperature. The implanted Sn and W atoms were entirely substitutional on Ti sites in the applied fluence region, where the radiation damage did not yet reach the random level. A large σ increase was observed for all implants at displacement per atom values (dpa) below 1. Above dpa = 1, σ reveals a saturation value of 0.3 Ω⁻¹ cm⁻¹ for Ar implants, while for W and Sn implants a further increase of σ up to 30 Ω⁻¹ cm⁻¹ was measured. Between 70 K and 293 K ln σ was proportional to T^−1/2, (Ar,W) and T^−1/4 (Sn), indicating that the transport mechanism is due to variable range hopping.     

Depth profiling study on the migration of tritium in titanium induced by deuterium-ion bombardment

A thin titanium layer with uniformly absorbed tritium (T/Ti ˜1.0) was bombarded by 390 keV D₃⁺ ions (130 keV per deuteron). Bombardment was performed at low (111 K) and room temperatures up to fluences of 5.9 × 10¹⁸ D/cm² and 3.0 × 10¹⁸ D/cm², respectively. Depth profiles of tritium up to a depth of 0.8 mg/cm² (˜1.8 μm) were measured and the change of the profile with fluence was investigated by means of the T(d, )n nuclear reaction. At both of the temperatures, a dip was formed on the depth profile of tritium at the depth around the projected range, indicating that the deuteron bombardment induced the migration of tritium against the concentration gradient. At the low temperature, the dip showed a gradual growth with fluence and saturation of the growth at the higher fluences, which could not be described by the existing model for isotope mixing. The spectrum of protons from the D(d, p)T reaction obtained in the same measurement suggested that the release of deuterium suddenly started at the final stage of the present bombardment. The dip formed at room temperature was larger than that at the low temperature. The migration of tritium induced by the bombardment is discussed on the basis of the experimental results obtained.     

Release of nitrogen from SiOxNy films during RBS measurement

We have found that nitrogen atoms are released very rapidly from ultrathin SiO_xN_y films (2.6 nm) during RBS measurement with 500 keV He⁺ ions. The release behavior strongly depends on the preparation technique of the SiO_xN_y films. There is no release from the film prepared by thermal nitridation of SiO₂, while 80% of the nitrogen atoms are released from the film prepared by plasma nitridation at a fluence of 1×10¹⁶ cm⁻². The release cross-section for plasma SiO_xN_y films is of the order of 10⁻¹⁶ cm². This large cross-section cannot be explained by a simple recoil mechanism. The nitrogen release is also observed under irradiation with 5–10 keV electrons though the cross-section is of the order of 10⁻¹⁹ cm². These findings suggest that the observed nitrogen release is an electronic excitation induced process.     

PECVD Si nitride and Si oxide layers — Hydrogen analysis and etching after ion implantation

lon-implantation-induced selective etching of dielectric materials is considerably diminished with increasing hydrogen content. Making use of the ¹H(¹⁵N,γ)¹²C resonance reaction, low-temperature PECVD Si oxide and Si nitride layers were observed to contain 12 and 23 at.% H, respectively. For different reagents etch rates were measured regarding the virgin and ion—implanted-He⁺ Ne⁺ at 60, 100 keV — PECVD films.     

Pumping experiment of water on B and LaB6 films with an electron beam evaporator

The pumping characteristic of water vapor on boron and lanthanum hexaboride films formed with an electron beam evaporator have been investigated in high vacuum between 10⁻⁴ and 10⁻³ Pa. The measured initial maximum pumping speeds of water for the fresh B or LaB₆ films with a deposition amount from 2.3 × 10²¹ to 6.7× 10²¹ molecules/m² separately formed on a substrate are 3.2–4.9 m³/sm², and the saturation values of adsorbed water on these films are 2.1 ×10²⁰−1.3 × 10²¹ H₂O molecules/m².     

XPS and optical studies of Xe-implanted and annealed YSZ single crystals

Xe⁺ ion implantation with 200 keV was completed at room temperature up to a fluence of 1 × 10¹⁷ ion/cm² in yttria-stabilized zirconia (YSZ) single crystals. Optical absorption and X-ray photoelectron spectroscopy (XPS) were used to characterize the changes of optical properties and charge state in the as-implanted and annealed crystals. A broad absorption band centered at 522 or 497 nm was observed in the optical absorption spectra of samples implanted with fluences of 1 × 10¹⁶ ion/cm² and 1 × 10¹⁷ ion/cm², respectively. These two absorption bands both disappeared due to recombination of color centers after annealing at 250 °C. XPS measurements showed two Gaussian components of O_1s spectrum assigned to Zr–O and Y–O, respectively, in YSZ single crystals. After ion implantation, these two peaks merged into a single peak with the increasing etching depth. However, this single peak split into two Gaussian components again after annealing at 250 °C. The concentration of Xe decreased drastically after annealing at 900 °C. And the XPS measurement barely detected the Xe. There was no change in the photoluminescence of YSZ single crystals with a fluence of 1 × 10¹⁷ ion/cm² after annealing up to 900 °C.     

Effects of ion implantation on poly(dimethylsilylene-co-methylphenylsilylene)

The effects of ion implantation on the electrical and structural properties of poly(dimethylsilylene-co-methylphenylsilylene), (DMMPS) thin films have been investigated. Ionic species of krypton, arsenic, fluorine, chlorine, and sulfur were implanted at energies ranging from 35 to 200 keV and with doses of up to 1 × 10¹⁶ ion cm². The conductivity of the polymer increased upon implantation reaching a maximum value of 9.6 × 10⁻⁶ (Ω cm)⁻¹ for the case of arsenic ion at a dose of 1 × 10¹⁶ ion cm² and energy of 100 keV. The results showed that ion implantation induced conduction in DMMPS was primarily due to structural modifications of the material brought about by the, energetic ions. Infrared analysis and Auger electron spectroscopy showed evidence for the formation of a silicon carbide-like structure upon implantation.     

Ion bombardment induced topography evolution on low index crystal surfaces of Cu and Pb

(100), (110) and (111) oriented single crystal surfaces of Cu and Pb have been bombarded with inert gas ions, self ions, ions of the other substrate species and Bi in the energy range 50–150 keV and in the fluence range 10¹⁵–10¹⁸ ions cm². The evolving surface topography was observed by scanning electron microscopy. This topography was observed to be strongly influenced by ion species and surface orientation but the habit of the topography was delineated at low fluences and the features increased in size and density with increasing fluence with some mutation to the more stable of the features. As an example Bi and Pb bombardment of (100) Cu leads to little topographic evolution, (110) Cu develops a system of parallel ridges with (100) facets and (111) Cu develops a prismatic surface, each prism possessing (100) facets. These, and the more general, results cannot be explained by surface erosion by sputtering theory alone (this predicts surface stability of the lowest sputtering yield orientation (110), nor by surface free energy density minimisation criteria (this predicts stability of (111) surfaces). It is proposed that the observed topography is most strongly related to the crystallographic form of precipitates of implanted species.     

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.     

Structural characterization of amorphous Fe–Si and its recrystallized layers

We have synthesized amorphous Fe–Si thin layers and investigated their microstructure using transmission electron microscopy (TEM). Si single crystals with (1 1 1) orientation were irradiated with 120 keV Fe⁺ ions to a fluence of 4.0 × 10¹⁷ cm⁻² at cryogenic temperature (120 K), followed by thermal annealing at 1073 K for 2 h. A continuous amorphous layer with a bilayered structure was formed on the topmost layer of the Si substrate in the as-implanted specimen: the upper layer was an amorphous Fe–Si, while the lower one was an amorphous Si. After annealing, the amorphous bilayer crystallized into a continuous β-FeSi₂ thin layer.     

Helium retention of vanadium alloy after energetic helium ion irradiation

Helium irradiation experiments of V–4Ti alloy were conducted in an ECR ion irradiation apparatus by using helium ions with energy of 5 keV. The ion fluence was in the range from 1 × 10¹⁷ He/cm² to 8 × 10¹⁷ He/cm². After the helium ion irradiation, the helium retention was examined by using a technique of thermal desorption spectroscopy (TDS). After the irradiation, the blisters with a size of about 0.1 μm were observed at the surface, and the blister density increased with the ion fluence. Two desorption peaks were observed at approximately 500 and 1200 K in the thermal desorption spectrum. When the ion fluence was low, the retained helium desorbed mainly at the higher temperature regime. As increase of the ion fluence, the desorption at the lower temperature peak increased and the retained amount of helium saturated. The saturated amount was approximately 2.5 × 10¹⁷ He/cm². This value was comparable with those of the other plasma facing materials such as graphite.     

A study of the blue photoluminescence emission from thermally-grown, Si-implanted SiO2 films after short-time annealing

Thermal SiO₂ films have been implanted with Si⁺ ions using double-energy implants (200 + 100 keV) at a substrate temperature of about −20°C to total doses in the range 1.6 × 10¹⁶−1.6 × 10¹⁷ cm⁻² followed by short-time thermal processing, in order to form a Si nanostructure capable of yielding blue photoluminescence (PL). The intensity and the peak position of the PL band have been investigated as a function of ion dose, manner of heat treatment, anneal time and anneal temperature. For the formation of blue PL emitting centres, optimum processing conditions in terms of excess Si concentration and overall thermal budget are mandatory. The nature of the observed blue emission is discussed.