Investigation of the effects of low energy high dose ion bombardment in metals and compound semiconductors

The effect of low energy nitrogen molecular ion beam bombardment on metals and compound semiconductors has been studied, with the aim to investigate at the effects of ion and target properties. For this purpose, nitrogen ion implantation in aluminium, iron, copper, gold, GaAs and AIGaAs is studied using XPS and Angle Resolve XPS. A series of experimental studies on N+2 bombardment induced compositional changes, especially the amount of nitrogen retained in the target, were accomplished. Both monoenergetic implantation and non-monoenergetic ion implantation were investigated, using the VG Scientific ESCALAB 200D system and a d. c. plasma cell, respectively. When the samples, with the exception of gold, are exposed to air, native oxide layers are formed on the surfaces. In the case of monoenergetic implantation, the surfaces were cleaned using Ar+ beam bombardment prior to implantation. The materials were then bombarded with N2+ beam and eight sets of successful experiments were performed on each sample, using a rastered N2+ ion beam of energy of 2, 3, 4 and 5 keV with current densities of 1 μA/cm2 and 5 μA/cm22 for each energy. The bombarded samples were examined by ARXPS. After each complete implantation, XPS depth profiles were created using Ar+ beam at energy 2 ke V and current density 2 μA/cm2 . As the current density was chosen as one of the parameters, accurate determination of current density was very important. In the case of glow discharge, two sets of successful experiments were performed in each case, by exposing the samples to nitrogen plasma for the two conditions: at low pressure and high voltage and high pressure and low voltage. These samples were then examined by ARXPS. On the theoretical side, the major problem was prediction of the number of ions of an element that can be implanted in a given matrix. Although the programme is essentially on experimental study, but an attempt is being made to understand the current theoretical models, such as SATVAL, SUSPRE and TRIM. The experimental results were compared with theoretical predictions, in order to gain a better understanding of the mechanisms responsible. From the experimental results, considering possible experimental uncertainties, there is no evidence of significant variation in nitrogen saturation concentration with ion energy or ion current density in the range of 2-5 ke V, however, the retention characteristics of implantant seem to strongly depend on the chemical reactivity between ion species and target material. The experimental data suggests the presence of at least one thermal process. The discrepancy between the theoretical and experimental results could be the inability of the codes to account for molecular ion impact and thermal processes.

Development and evaluation of an ion induced x-ray emission system for the analysis of light and medium weight elements

The present work describes the development of a proton induced X-ray emission (PIXE) analysis system, especially designed and builtfor routine quantitative multi-elemental analysis of a large number of samples. The historical and general developments of the analytical technique and the physical processes involved are discussed. The philosophy, design, constructional details and evaluation of a versatile vacuum chamber, an automatic multi-sample changer, an on-demand beam pulsing system and ion beam current monitoring facility are described.The system calibration using thin standard foils of Si, P, S,Cl, K, Ca, Ti, V, Fe, Cu, Ga, Ge, Rb, Y and Mo was undertaken at proton beam energies of 1 to 3 MeV in steps of 0.5 MeV energy and compared with theoretical calculations. An independent calibration check using bovine liver Standard Reference Material was performed.  The minimum detectable limits have been experimentally determined at detector positions of 90° and 135° with respect to the incident beam for the above range of proton energies as a function of atomic number Z. The system has detection limits of typically 10- 7 to 10- 9 g for elements 14ions of areal density of thin foils using Rutherford backscattering data.  Amniotic fluid samples supplied by South Sefton Health Authority were successfully analysed for their low base line elemental concentrations. In conclusion the findings of this work are discussed with suggestions for further work .

Ion bombardment induced compositional changes in compound semiconductor surfaces studied by XPS combined with LEISS

Surface compositional change of GaP, GaAs, GaSb, InP, InAs, InSb, GeSi and CdSe single crystals due to low keV noble gas ion beam bombardment has been investigated by combining X-ray Photoelectron Spectroscopy (XPS) and Low Energy Ion Scattering Spectroscopy (LEISS). The purpose of using this complementary analytical method is to obtain more complete experimental evidence of ion beam modification in surfaces of compound semiconductors and GeSi alloy to improve the understanding of the mechanisms responsible for these effects. Before ion bombardment the sample surfaces were analysed nondestructively by Angular Resolved XPS (ARXPS) and LEISS to get the initial distribution of surface composition. Ion bombardment experiments were carried out using 3keV argon ions with beam current of 1μA for a period of 50 minutes, compositional changes in the surfaces of compound semiconductors and GeSi alloy were monitored with normal XPS. After ion bombardment the surfaces were re-examined with ARXPS and LEISS. Both XPS and LEISS results showed clearly that ion bombardment will change the compositional distribution in the compound semiconductor and GeSi surfaces. In order to explain the observed experimental results, two major theories in this field, Sigmund linear collision cascade theory and the thermodynamic models based on bombardment induced Gibbsian surface segregation and diffusion, were investigated. Computer simulation using TRIM code was also carried out for assistance to the theoretical analysis. Combined the results obtained from XPS and LEISS analyses, ion bombardment induced compositional changes in compound semiconductor and GeSi surfaces are explained in terms of the bombardment induced Gibbsian surface segregation and diffusion.

Oxygen effects on irradiated tantalum alloys

Ta and Ta-1% W are being considered to be used as target clad materials in the LANSCE proton beam line for the material test station (MTS). To investigate the embrittlement of these materials due to oxygen contamination and proton irradiation, Ta and Ta-1 wt% W (as received and with ~400 ppm O) were exposed to a 3.5 MeV proton beam at the ion beam materials laboratory at LANL. After irradiating the samples in the proton beam, nanoindentation was performed in cross-section to investigate the hardness increase of the materials due to irradiation. The nanoindentation showed that the hardness increase due to irradiation is between 9% and 20% depending on the material. The results show good agreement with mechanical testing results on tantalum and Ta-1 wt% W after high energy proton irradiation to doses up to 23 dpa.

Wear of abrasion resisting materials

The wear behaviour of a series of chromium containing white irons has been investigated under conditions of high stress grinding abrasion using a specimen on track abrasion testing machine. The measured abrasion resistance of the irons has been explained in terms of microstructure and hardness and with respect to the wear damage observed at and beneath abraded surfaces. During abrasion material removal occurred by cracking and detachment from the matrix of eutectic carbides as well as by penetration and micromachining effects of the abrasive grits being crushed at the wearing surface. Under the particular test conditions used martensitic matrix structures gave higher resistance to abrasion than austenitic or pearlitic. However, no simple relationship was found between general hardness or matrix microhardness at wear surfaces and abrasion resistance, and the test yielded pessimistic results for austenitic irons. The fine structures of the 15% Cr and 30% Cr alloys were studied by thin foil transmission electron microscopy. It was found that both the matrix and carbide constituents could be thinned for examination at 100 Kv using conventional dishing followed by ion beam thinning. Flany of the rodlike eutectic N7C3 carbides were seen to consist of clusters of scalier rods with individual 117C3 crystals quite often containing central cores of matrix constituent. 3oth eutectic and secondary N7C3 carbides were found to contain stacking faults on planes normal to the basal plane. In the eutectic carbides in the 30A Cr iron there was evidence of an in-situ PI7C3 C. transition which had taken place during the hardening heat treatment of this alloy. In the as-cast austenitic matrix iron strain induced martensite was produced at the wear surface contributing to work hardening. The significance of these findings have been discussed in relation to wear performance.

A micro-compression study of shape-memory deformation in U-13 at.% Nb

Microcompression specimens, 10–15 µm in diameter by 20–30 µm in height, were produced from individual parent grains in a polycrystalline U–13 at.%Nb shape-memory alloy using the focused ion beam technique. The specimens were tested in a nanoindentation instrument with a flat diamond tip to investigate stress–strain behavior as a function of crystallographic orientation. The results are in qualitative agreement with a single-crystal accommodation strain (Bain strain) model of the shape-memory effect for this alloy.

Increasing the fracture toughness of silicon by ion implantation

Previous studies have shown that moderate doses of radiation can lead to increased fracture toughness in ceramics. An experimental investigation was conducted to determine the effects of ion implantation on fracture toughness in silicon. Specimens implanted with Ne showed increased fracture toughness, over the entire range of implantations tested. Using ions of various energies to better distribute implantation damage further increased the fracture toughness even though the region of amorphous damage was slightly decreased. The implantation damage accumulated in a predictable manner so that fracture toughness could be optimized.

Surface roughness reduction and diffraction efficiency optimisation for e-beam written phase masks

We report the control of surface relief grating parameters and roughness for phase masks produced using e-beam lithography (EBL) and reactive ion etching (RIE). The relationships between processing conditions, grating parameters, surface roughness and the diffraction efficiency of the zeroth and the two first order transmitted beams are discussed.

Development of an on-demand beam pulsing system for Pixe-analysis of thick targets

This work concerns the developnent of a proton irduced X-ray emission (PIXE) analysis system and a multi-sample scattering chamber facility. The characteristics of the beam pulsing system and its counting rate capabilities were evaluated by observing the ion-induced X-ray emission from pure thick copper targets, with and without beam pulsing operation. The characteristic X-rays were detected with a high resolution Si(Li) detector coupled to a rrulti-channel analyser. The removal of the pile-up continuum by the use of the on-demand beam pulsing is clearly demonstrated in this work. This new on-demand pu1sirg system with its counting rate capability of 25, 18 and 10 kPPS corresponding to 2, 4 am 8 usec main amplifier time constant respectively enables thick targets to be analysed more readily. Reproducibility tests of the on-demard beam pulsing system operation were checked by repeated measurements of the system throughput curves, with and without beam pulsing. The reproducibility of the analysis performed using this system was also checked by repeated measurements of the intensity ratios from a number of standard binary alloys during the experimental work. A computer programme has been developed to evaluate the calculations of the X-ray yields from thick targets bornbarded by protons, taking into account the secondary X-ray yield production due to characteristic X-ray fluorescence from an element energetically higher than the absorption edge energy of the other element present in the target. This effect was studied on metallic binary alloys such as Fe/Ni and Cr/Fe. The quantitative analysis of Fe/Ni and Cr/Fe alloy samples to determine their elemental composition taking into account the enhancement has been demonstrated in this work. Furthermore, the usefulness of the Rutherford backscattering (R.B.S.) technique to obtain the depth profiles of the elements in the upper micron of the sample is discussed.

Nitrogen implantation of tool steels and engineering coatings

Ion implantation modifies the surface composition and properties of materials by bombardment with high energy ions. The low temperature of the process ensures the avoidance of distortion and degradation of the surface or bulk mechanical properties of components. In the present work nitrogen ion implantation at 90 keV and doses above 1017 ions/cm2 has been carried out on AISI M2, D2 and 420 steels and engineering coatings such as hard chromium, electroless Ni-P and a brush plated Co-W alloy. Evaluation of wear and frictional properties of these materials was performed with a lubricated Falex wear test at high loads up to 900 N and a dry pin-on-disc apparatus at loads up to 40 N. It was found that nitrogen implantation reduced the wear of AISI 420 stainless steel by a factor of 2.5 under high load lubricated conditions and by a factor of 5.5 in low load dry testing. Lower but significant reductions in wear were achieved for AISI M2 and D2 steels. Wear resistance of coating materials was improved by up to 4 times in lubricated wear of hard Cr coatings implanted at the optimum dose but lower improvements were obtained for the Co-W alloy coating. However, hardened electroless Ni-P coatings showed no enhancement in wear properties. The benefits obtained in wear behaviour for the above materials were generally accompanied by a significant decrease in the running-in friction. Nitrogen implantation hardened the surface of steels and Cr and Co-W coatings. An ultra-microhardness technique showed that the true hardness of implanted layers was greater than the values obtained by conventional micro-hardness methods, which often result in penetration below the implanted depth. Scanning electron microscopy revealed that implantation reduced the ploughing effect during wear and a change in wear mechanism from an abrasive-adhesive type to a mild oxidative mode was evident. Retention of nitrogen after implantation was studied by Nuclear Reaction Analysis and Auger Electron Spectroscopy. It was shown that maximum nitrogen retention occurs in hard Cr coatings and AISI 420 stainless steel, which explains the improvements obtained in wear resistance and hardness. X-ray photoelectron spectroscopy on these materials revealed that nitrogen is almost entirely bound to Cr, forming chromium nitrides. It was concluded that nitrogen implantation at 90 keV and doses above 3x1017 ions/cm2 produced the most significant improvements in mechanical properties in materials containing nitride formers by precipitation strengthening, improving the load bearing capacity of the surface and changing the wear mechanism from adhesive-abrasive to oxidative.

Ion plating

Under ideal conditions ion plating produces finely grained dense coatings with excellent adhesion. The ion bombardment induced damage initiates a large number of small nuclei. Simultaneous coating and sputtering stimulates high rates of diffusion and forms an interfacial region of graded composition responsible for good adhesion. To obtain such coatings on components far industrial applications, the design and construction Of an ion plater with a 24" (O.6rn) diameter chamber were investigated and modifications of the electron beam gun were proposed. A 12" (O.3m) diameter ion plater was designed and constructed. The equipment was used to develop surfaces for solar energy applications. The conditions to give extended surfaces by sputter etching were studied. Austenitic stainless steel was sputter etched at 20 and 30 mTorr working pressure and at 3, 4 and 5 kV. Uniform etching was achieved by redesigning the specimen holder to give a uniform electrostatic field over the surfaces of the specimens. Surface protrusions were observed after sputter etching. They were caused by the sputter process and were independent of grain boundaries, surface contaminants and inclusions. The sputtering rate of stainless steel was highly dependent on the background pressure which should be kept below 10-5 Torr. Sputter etching improved the performance of stainless steel used as a solar selective surface. A twofold improvement was achieved on sputter etching bright annealed stainless steel. However, there was only slight improvement after sputter etching stainless steel which had been mechanically polished to a mirror finish. Cooling curves Were used to measure the thermal emittance of specimens.The deposition rate of copper was measured at different levels of power input and was found to be a maximum at 9.5 kW. The diameter of the copper feed rod was found to be critical for the maintenance of a uniform evaporation rate.

Cracking in hydrogen ion-implanted Si/Si0.8Ge0.2/Si heterostructures

We demonstrate that a controllable cracking can be realized in Si with a buried strain layer when hydrogen is introduced using traditional H-ion implantation techniques. However, H stimulated cracking is dependent on H projected ranges; cracking occurs along a Si0.8Ge0.2 strain layer only if the H projected range is shallower than the depth of the strained layer. The absence of cracking for H ranges deeper than the strain layer is attributed to ion-irradiation induced strain relaxation, which is confirmed by Rutherford-backscattering-spectrometry channeling angular scans. The study reveals the importance of strain in initializing continuous cracking with extremely low H concentrations.

Size-dependent radiation tolerance in ion irradiated TiN/AlN nanolayer films

Interface effects on ion-irradiation tolerance properties are investigated in nanolayered TiN/AlN films with individual layer thickness varied from 5 nm to 50 nm, prepared by pulsed laser deposition. Evolution of the microstructure and hardness of the multilayer films are examined on the specimens before and after He ion-implantation to a fluence of 4 × 10 m at 50 keV. The suppression of amorphization in AlN layers and the reduction of radiation-induced softening are observed in all nanolayer films. A clear size-dependent radiation tolerance characteristic is observed in the nanolayer films, i.e., the samples with the optimum layer thickness from 10 nm to 20 nm show the best ion irradiation tolerance properties, and a critical layer thickness of more than 5 nm is necessary to prevent severe intermixing. This study suggests that both the interface characteristics and the critical length scale (layer thickness) contribute to the reduction of the radiation-induced damages in nitride-based ceramic materials. © 2013 Elsevier B.V. All rights reserved.

Surface roughness reduction and diffraction efficiency optimisation for e-beam written phase masks

We report the control of surface relief grating parameters and roughness for phase masks produced using e-beam lithography (EBL) and reactive ion etching (RIE). The relationships between processing conditions, grating parameters, surface roughness and the diffraction efficiency of the zeroth and the two first order transmitted beams are discussed.

Heavy ion irradiation effects in zirconium nitride

Polycrystalline zirconium nitride (ZrN) samples were irradiated with He +, Kr ++, and Xe ++ ions to high (>1·10 16 ions/cm 2) fluences at ∼100 K. Following ion irradiation, transmission electron microscopy (TEM) and grazing incidence X-ray diffraction (GIXRD) were used to analyze the microstructure and crystal structure of the post-irradiated material. For ion doses equivalent to approximately 200 displacements per atom (dpa), ZrN was found to resist any amorphization transformation, based on TEM observations. At very high displacement damage doses, GIXRD measurements revealed tetragonal splitting of some of the diffraction maxima (maxima which are associated with cubic ZrN prior to irradiation). In addition to TEM and GIXRD, mechanical property changes were characterized using nanoindentation. Nanoindentation revealed no change in elastic modulus of ZrN with increasing ion dose, while the hardness of the irradiated ZrN was found to increase significantly with ion dose. Finally, He + ion implanted ZrN samples were annealed to examine He gas retention properties of ZrN as a function of annealing temperature. He gas release was measured using a residual gas analysis (RGA) spectrometer. RGA measurements were performed on He-implanted ZrN samples and on ZrN samples that had also been irradiated with Xe ++ ions, in order to introduce high levels of displacive radiation damage into the matrix. He evolution studies revealed that ZrN samples with high levels of displacement damage due to Xe implantation, show a lower temperature threshold for He release than do pristine ZrN samples.