Dissertations / Theses on the topic 'Swift Heavy Ions'

Today, the dominating way of patterning nanosystems is by irradiation-based lithography (e-beam, DUV, EUV, and ions). Compared to the other irradiations, ion tracks created by swift heavy ions in matter give the highest contrast, and its inelastic scattering facilitate minute widening and high aspect ratios (up to several thousands). Combining this with high resolution masks it may have potential as lithography technology for nanotechnology. Even if this ‘ion track lithography’ would not give a higher resolution than the others, it still can pattern otherwise irradiation insensitive materials, and enabling direct lithographic patterning of relevant material properties without further processing. In this thesis ion tracks in thin films of polyimide, amorphous SiO₂ and crystalline TiO₂ were made. Nanopores were used as templates for electrodeposition of nanowires.

In lithography patterns are defined by masks. To write a nanopattern onto masks e-beam lithography is used. It is time-consuming since the pattern is written serially, point by point. An alternative approach is to use self-assembled patterns. In these first demonstrations of ion track lithography for micro and nanopatterning, self-assembly masks of silica microspheres and porous alumina membranes (PAM) have been used.

For pattern transfer, different heavy ions were used with energies of several MeV at different fluences. The patterns were transferred to SiO₂ and TiO₂. From an ordered PAM with pores of 70 nm in diameter and 100 nm inter-pore distances, the transferred, ordered patterns had 355 nm deep pores of 77 nm diameter for SiO₂ and 70 nm in diameter and 1,100 nm deep for TiO₂. The TiO₂ substrate was also irradiated through ordered silica microspheres, yielding different patterns depending on the configuration of the silica ball layers.

Finally, swift heavy ion irradiation with high fluence (above 10¹⁵/cm²) was assisting carbon nanopillars deposition in a PAM used as template.

Indium phosphide (InP) is an important III-V compound, with a variety of applications, for example, in light emitting diodes (LED), InP based photonic crystals and in semiconductor lasers, heterojunction bipolar transistors in integrated circuit applications and in transistors for microwave and millimeter-wave systems. The optical and electrical properties of this compound can be further tailored by ion implantation or prospectively by swift heavy ion beams. ¶ Thus knowledge of ion-induced disorder in this material is of important fundamental and practical interest. However, the disorder produced during heavy ion irradiation and the subsequent damage accumulation and recovery in InP is far from being completely understood. In terms of the damage accumulation mechanisms, the conclusions drawn in the numerous studies performed have often been in conflict with one another. A factor contributing to the uncertainties associated with these conflicting results is a lack of information and direct observation of the “building blocks” leading to the ultimate damage created at high ion fluences as an amorphous layer. These building blocks formed at lower fluence regimes by single ion impacts can be directly observed as isolated disordered zones and ion tracks for low energy and swift heavy ion irradiation, respectively. ¶ The primary aim of this work has thus been to obtain a better understanding of the disorder in this material through direct observations and investigation of disorder produced by individual heavy ions in both energy regimes (i.e. elastic and inelastic energy deposition regimes) especially with low ion fluence irradiations. In this thesis the heavy ion induced disorder introduced by low energy Au ions (100 keV Au+) and high energy Au (200 MeV Au+16) ion irradiation in InP were investigated using Transmission Electron Microscopy (TEM), Rutherford Backscattering Spectrometry (RBS/C) and Atomic Force Microscopy (AFM). ¶ The accumulation of damage due to disordered zones and ion tracks is described and discussed for both low energy and swift ion irradiation respectively. ¶ The in-situ TEM annealing of disordered zones created by 100 keV Au+ ion irradiation shows that these zones are sensitive to electron beam irradiation and anneal under electron energies not sufficient to elastically displace lattice atoms, i.e. subthreshold energies for both constituent atoms In and P. ¶ Ion tracks due to swift heavy ion irradiation were observed in this material and the interesting track morphology was described and discussed. The surface nanotopographical changes due to increasing fluence of swift heavy ions were observed by AFM where the onset of large increase in surface roughness for fluences sufficient to cause complete surface amorphization was observed. ¶ In addition to InP, the principle material of this project, a limited amount of TEM observation work has been performed on several other important compounds (apatite and monazite) irradiated by 200 MeV Au+ ions for comparative purposes. Again the observed segmental morphology of ion tracks were shown and possible track formation scenario and structure were discussed and similarities were drawn to the previously observed C60 cluster ion tracks in CaF2 as more knowledge and data base exist about defect dynamics and formation in that material.

ZrN has been identified as a candidate material for use as an inert matrix fuel host for the transmutation of plutonium and minor actinides. These materials will be subjected to large amounts of different types of radiation within the nuclear reactor core. The types of radiation include fission fragments and alpha-particles amongst others. Recent studies suggest that nanocrystalline material may have a higher radiation tolerance than their polycrystalline and bulk counterparts. Some studies have shown that swift heavy ion irradiation may also significantly modulate hydrogen and helium behaviour in materials. This phenomenon is also of considerable practical interest for inert matrix fuel hosts, since these materials accumulate helium via (n,) reactions and will also be subjected to irradiation by fission fragments. The aim of this investigation is therefore to study the effects of fission fragment and alpha particle irradiation on nanocrystalline ZrN. In an effort to simulate the effects of fission fragments on nanocrystalline zirconium nitride different layers (on a Si substrate) of various thicknesses (0.1, 3, 10 and 20 μm) were irradiated with 167 MeV Xe, 250 MeV Kr and 695 MeV Bi ions to fluences in the range from 31012 to 2.61015 cm-2 for Xe, 1×1013 to 7.06×1013 cm-2 for Kr and 1012 to 1013 cm-2 for Bi. The purpose of this irradiation is to simulate the effects of fission fragments on nanocrystalline ZrN. In order to simulate the effects of alpha particles and the combined effects of alpha particles and fission fragments on nanocrystalline ZrN it was irradiated with 30 keV He to fluences between 1016 and 5×1016 cm-2, 167 MeV Xe to fluences between 5×1013 and 1014 cm-2 and also 695 MeV Bi to a fluence of 1.5×1013 cm-2. He/Bi and He/Xe irradiated samples were annealed at temperatures between 600 and 1000 °C. The different irradiated layers were subsequently analysed via X-ray diffraction (XRD), μ-Raman, transmission electron microscopy (TEM) and nano indentation hardness testing (NIH) techniques. XRD, TEM, μ-Raman and NIH results indicate that ZrN has a very high tolerance to the effects of high energy irradiation. The microstructure of nanocrystalline ZrN remains unaffected by electronic excitation effects even at a very high stopping power. TEM and SEM results indicated that post irradiation heat treatment induces exfoliation at a depth that corresponds to the end-of-range of 30 keV He ions. Results from He/Xe irradiated samples revealed that electronic excitation effects, due to Xe ions, suppress helium blister formation and consequently the exfoliation processes. He/Bi samples however do not show the same effects, but this is possibly due to the lower fluence of Bi ions. This suggests that nanocrystalline ZrN is prone to the formation of He blisters which may ultimately lead material failure. These effects may however be mitigated by electronic excitation effects from certain SHIs.

In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1×1010 – 5×1012 ions/cm2). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic species. While the irradiation of polymers with high energy heavy ions represents a enforced simulation test of the radiation damage in accelerators, they correspond to real situation in space where devices are directly being hit by very high energy heavy ions.

Philosophiae Doctor - PhD
The combination of ion track technology and chemical etching as a tool to enhance polymer gas properties such as permeability and selectivity is regarded as an avenue to establish technology commercialization and enhance applicability. Traditionally, permeability and selectivity of polymers have been major challenges especially for gas applications. However, it is important to understand the intrinsic polymer properties in order to be able to predict or identify their possible ion-polymer interactions thus facilitate the reorientation of existing polymer structural configurations. This in turn can enhance the gas permeability and selectivity properties of the polymers. Therefore, the choice of polymer is an important prerequisite. Polyethylene terephthalate (PET) belongs to the polyester group of polymers and has been extensively studied within the context of post-synthesis modification techniques using swift heavy ion irradiation and chemical treatment which is generally referred to as ‘track-etching’. The use of track-etched polymers in the form of symmetrical membranes structures to investigate gas permeability and selectivity properties has proved successful. However, the previous studies on track-etched polymers films have been mainly focused on the preparation of symmetrical membrane structure, especially in the case of polyesters such as PET polymer films. Also, polyolefins such as polymethyl pentene (PMP) have not been investigated using swift heavy ions and chemical etching procedures. In addition, the use of ‘shielded’ material on PET and PMP polymer films prior to swift heavy ion irradiation and chemical etching to prepare asymmetrical membrane structure have not been investigated. The gas permeability and selectivity of the asymmetrical membrane prepared from swift heavy ion irradiated etched 'shielded' PET and PMP polymer films have not been determined. These highlighted limitations will be addressed in this study. The overall objective of this study was to prepare asymmetric polymeric membranes with porous surface on dense layer from two classes of polymers; (PET and PMP) in order to improve their gas permeability and selectivity properties. The research approach in this study was to use a simple and novel method to prepare an asymmetric PET and PMP polymer membrane with porous surface and dense layer by mechanical attachment of ‘shielded’ material on the polymer film before swift heavy ion irradiation. This irradiation approach allowed for the control of swift heavy ion penetration depth into the PET and PMP polymer film during irradiation. The procedure used in this study is briefly described. Commercial PET and PMP polymer films were mechanically ‘shielded’ with aluminium and PET foils respectively. The ‘shielded’ PET polymer films were then irradiated with swift heavy ions of Xe source while ‘shielded’ PMP polymer films were irradiated with swift heavy ions Kr. The ion energy and fluence of Xe ions was 1.3 MeV and 106 respectively while the Kr ion energy was 3.57 MeV and ion fluence of 109. After swift heavy ion irradiation of ‘shielded’ PET and PMP polymer films, the attached ‘shielded’ materials were removed from PET and PMP polymer film and the irradiated PET and PMP polymer films were chemically etched in sodium hydroxide (NaOH) and acidified chromium trioxide (H2SO4 + CrO3) respectively. The chemical etching conditions of swift heavy ion irradiated ‘shielded’ PET was performed with 1 M NaOH at 80 ˚C under various etching times of 3, 6, 9 and 12 minutes. As for the swift heavy ion irradiated ‘shielded’ PMP polymer film, the chemical etching was performed with 7 M H2SO4 + 3 M CrO3 solution, etching temperature was varied between 40 ˚C and 80 ˚C while the etching time was between 40 minutes to 150 minutes. The SEM (surface and cross-section micrograph) morphology results of the swift heavy ion irradiated ‘shielded’ etched PET and PMP films showed that asymmetric membranes with a single-sided porous surface and dense layer was prepared and remained unchanged even after 12 minutes of etching with 1 M NaOH solution as in the case of PET and 2 hours 30 minutes of etching with 7 M H2SO4 + 3 M CrO3 as observed for PMP polymer film. Also, the swift heavy ion irradiated ‘shielded’ etched PET polymer film showed the presence of pores on the polymer film surface within 3 minutes of etching. After 12 minutes chemical etching with 1 M NaOH solution, the dense layer of swift heavy ion irradiated ‘shielded’ etched PET polymer film experienced significant reduction in thickness of about 40 % of the original thickness of as-received PET polymer film. The surface morphology of swift heavy ion irradiated ‘shielded’ etched PET polymer film by SEM analysis revealed finely distributed pores with spherical shapes for the swift heavy ion irradiated ‘shielded’ etched PET polymer film within 6 minutes of etching with 1 M NaOH solution. Also, after 9 minutes and 12 minutes of etching with 1 M NaOH solution of the swift heavy ion irradiated ‘shielded’ etched PET polymer film, the pore walls experienced complete collapse with intense surface roughness. Interestingly, the 12 minutes etched swift heavy ion ‘shielded’ irradiated PET did not lose its asymmetrical membrane structure despite the collapse of the pore walls. In the case of swift heavy ion irradiated ‘shielded’ etched PMP polymer film, SEM morphology analysis showed that the pores retained their shape with the presence of defined pores without intense surface roughness even after extended etching with 7 M H2SO4 + 3 M CrO3 for 2 hours 30 minutes. Also, the pores of swift heavy ion irradiated ‘shielded’ etched PMP polymer films were observed to be mono dispersed and not agglomerated or overlapped. The SEM cross-section morphology of the swift heavy ion irradiated ‘shielded’ etched PMP polymer film showed radially oriented pores with increased pore diameters in the PMP polymer film which indicated that etching was radial instead of lateral, and no through pores were observed showing that the dense asymmetrical structure was retained. The SEM results revealed that the pore morphology i.e. size and shape could be accurately controlled during chemical etching of swift heavy ion ‘shielded’ irradiated PET and PMP polymer films. The XRD results of swift heavy ion irradiated ‘shielded’ etched PET revealed a single diffraction peak for various times of chemical etching in 1 M NaOH solution at 3, 6, 9 and 12 minutes. The diffraction peak of swift heavy ion irradiated ‘shielded’ etched PET was observed to reduce in intensity and marginally shifted to lower angles from 25.95˚ 2 theta to 25.89˚ 2 theta and also became broad in shape. It was considered that the continuous broadening of diffraction peaks due to an increase in etching times could be attributed to disorderliness of the ordered region within the polymer matrix and thus decreases in crystallinity of the swift heavy ion irradiated ‘shielded’ etched PET polymer film. The XRD analysis of swift heavy ion irradiated ‘shielded’ etched PMP polymer films indicated the presence of the diffraction peak at 9.75˚ 2 theta with decrease in intensity while the diffraction peaks located at 13.34˚, 16.42˚, 18.54˚ and 21.46˚ 2 theta disappeared after chemical etching in acidified chromium trioxide (H2SO4 + CrO3) after 2 hours 30 minutes. The TGA thermal profile analysis of swift heavy ion irradiated ‘shielded’ etched PET did not show the evolution of volatile species or moisture at lower temperatures even after 12 minutes of etching in 1 M NaOH solution in comparison with commercial PET polymer film. Also, it was observed that the swift heavy ion irradiated layered’ etched PET polymer film started to undergo degradation at a higher temperature than untreated PET which resulted in an approximate increase of 50 ˚C in comparison with the commercial PET polymer film. The TGA results of swift heavy ion irradiated ‘shielded’ etched PMP polymer film revealed an improvement of about 50 ˚C in thermal stability before thermal degradation even after etching in acidified chromium trioxide for 2 hours 30 minutes at 80 ˚C. Spectroscopy (IR) analysis of the swift heavy ion irradiated ‘shielded’ etched PET and PMP polymer films showed the presence of characteristic functional groups associated with either PET or PMP structures. The variations of irradiation and chemical etching conditions revealed that the swift heavy ion ‘shielded’ irradiated etched PET polymer film experienced continuous degradation of available functional groups as a function of etching time and also with complete disappearance of some functional groups such as 1105 cm-1 and 1129 cm-1 compared with the as-received PET polymer film which are both associated with the para-substituted position of benzene rings. In the case of swift heavy ion irradiated ‘shielded’ etched PMP polymer film, spectroscopic (IR) analysis showed significant variations in the susceptibility of associated functional groups within the PMP polymer film with selective attack and emergence of some specific functional groups such as at 1478 cm-1, 1810 cm-1 and 2115 cm-1 which were assigned to methylene, CH3 (asymmetry deformation), CH3 and CH2 respectively Also, the IR results for swift heavy ion irradiated ‘shielded’ etched PMP polymer showed that unsaturated olefinic groups were the dominant functional groups that were being attacked by during etching with acidified chromium trioxide (H2SO4+CrO3) which is an aggressive chemical etchant. The gas permeability analysis of swift heavy ion irradiated ‘shielded’ etched PET and PMP polymer films showed that the gas permeability was improved in comparison with the as-received PET and as-received PMP polymer films. The gas permeability of swift heavy ion irradiated ‘shielded’ etched PET increased as a function of etching time and was found to be highest after 12 minutes of chemical etching in 1 M NaOH at 80 ˚C. In the case of swift heavy ion irradiated ‘shielded’ etched PMP, the gas permeability was observed to show the highest gas permeability after 2 hours 30 minutes of etching in H2SO4 + CrO3 solution. The gas permeability analysis for swift heavy ion irradiated ‘shielded’ PET and PMP polymer films was tested for He, CO2 and CH4 and the permeability results showed that helium was most permeable compared with CO2 and CH4 gases. In comparison, the selectivity analysis was performed for He/CO2 and CH4/He and the results showed that the selectivity decreased with increasing in etching time as expected. This study identified some important findings. Firstly, it was observed that the use of ‘shielded’ material on PET and PMP polymer films prior to swift heavy ion irradiation proved successful in the creation of asymmetrical polymer membrane structure. Also, it was also observed that the chemical etching of the ‘shielded’ swift heavy ion irradiated PET and PMP polymer films resulted in the presence of pores on the swift heavy ion irradiated side while the unirradiated sides of the PET and PMP polymer films were unaffected during chemical etching hence the pore depth could be controlled. In addition, the etching experiment showed that the pores geometry can be controlled as well as the gas permeability and selectivity properties of swift heavy ion ‘shielded’ irradiated etched PET and PMP polymer films. The process of polymer bulk and surface properties modification using ion-track technology i.e. swift heavy ion irradiation and subsequent chemical treatment of the irradiated polymer serves to reveal characteristic pore profiles unique to the prevailing ion-polymer interaction and ultimately results in alteration of the polymer characteristics.

Graphite is a classical material in neutron radiation environments, being widely used in nuclear reactors and power plants as a moderator. For high energy particle accelerators, graphite provides ideal material properties because of the low Z of carbon and its corresponding low stopping power, thus when ion projectiles interact with graphite is the energy deposition rather low. This work aims to improve the understanding of how the irradiation with swift heavy ions (SHI) of kinetic energies in the range of MeV to GeV affects the structure of graphite and other carbon-based materials. Special focus of this project is given to beam induced changes of thermo-mechanical properties. For this purpose the Highly oriented pyrolytic graphite (HOPG) and glassy carbon (GC) (both serving as model materials), isotropic high density polycrystalline graphite (PG) and other carbon based materials like carbon fiber carbon composites (CFC), chemically expanded graphite (FG) and molybdenum carbide enhanced graphite composites (MoC) were exposed to different ions ranging from 131Xe to 238U provided by the UNILAC accelerator at GSI in Darmstadt, Germany. To investigate structural changes, various in-situ and off-line measurements were performed including Raman spectroscopy, x-ray diffraction and x-ray photo-electron spectroscopy. Thermo-mechanical properties were investigated using the laser-flash-analysis method, differential scanning calorimetry, micro/nano-indentation and 4-point electrical resistivity measurements. Beam induced stresses were investigated using profilometry. Obtained results provided clear evidence that ion beam-induced radiation damage leads to structural changes and degradation of thermal, mechanical and electrical properties of graphite. PG transforms towards a disordered sp2 structure, comparable to GC at high fluences. Irradiation-induced embrittlement is strongly reducing the lifetime of most high-dose exposed accelerator components. For irradiation temperatures above 200 °C damage formation is mitigated due to defect annealing. Thus a controlled temperature of accelerator components is desirable in order to increase the lifetime. This thesis contributes to a better understanding of radiation damage in swift heavy ion-exposed graphite with the aim to optimize the design of beam catchers and production targets for secondary ion beams for the Super Fragment Separator (Super-FRS) at FAIR. Moreover, the results of this work provide important input data for simulations to describe the beam response and lifetime of high-dose exposed critical accelerator components.

This work is devoted to the study of radiation damage produced by swift heavy ions in rare earth phosphates, materials that are considered as perspective for radioactive waste storage. Single crystals of rare earth phosphates were exposed to 2.1 GeV gold (Au) and 1.5 GeV xenon (Xe) ions of and analyzed mainly by Raman spectroscopy. All phosphates were found almost completely amorphous after the irradiation by 2.1 GeV Au ions at a fluence of 10^13 ions/cm^2. Radiation-induced changes in the Raman spectra include the intensity decrease of all Raman bands accompanied by the appearance of broad humps and a reduction of the pronounced luminescence present in virgin samples. Analyzing the Raman peak intensities as a function of irradiation fluence allowed the calculation of the track radii for 2.1 GeV Au ions in several rare earth phosphates, which appear to be about 5.0 nm for all studied samples. Series of samples were studied to search for a trend of the track radius depending on the rare earth element (REE) cation. Among the monoclinic phosphates both Raman and small-angle X-ray scattering (SAXS) suggest no significant change of the track radius with increasing REE mass. In contrast, within the tetragonal phosphates Raman spectroscopy data suggests a possible slight decreasing trend of the track radius with the increase of REE atomic number. That finding, however, requires further investigation due to the low reliability of the qualitative Raman analysis. Detailed analysis of Raman spectra in HoPO4 showed the increase of peak width at the initial stage of the irradiation and subsequent decrease to a steady value at higher fluences. This observation suggested the existence of a defect halo around the amorphous tracks in HoPO4. Raman peaks were found to initially shift to lower wavenumbers with reversing this trend at the fluence of 5x10^11 for NdPO4 and 10^12 ions/cm^2 for HoPO4. At the next fluence steps peaks moved in the other direction, passed positions assigned for virgin materials and moved even further at the fluence step of 10^13 ions/cm^2. This study has also shown that variation of beam parameters could drastically affect material degradation. Increase of Au ion flux was shown to produce partial sample annealing, most likely due to macroscopic temperature increase. At the same time the increase of 1.5 GeV Xe ion beam pulse intensity was shown to invoke enhanced amorphization in comparison to beams of low pulse intensity.

Indium phosphide (InP) is an important III-V compound, with a variety of applications, for example, in light emitting diodes (LED), InP based photonic crystals and in semiconductor lasers, heterojunction bipolar transistors in integrated circuit applications and in transistors for microwave and millimeter-wave systems. The optical and electrical properties of this compound can be further tailored by ion implantation or prospectively by swift heavy ion beams. ¶ Thus knowledge of ion-induced disorder in this material is of important fundamental and practical interest. However, the disorder produced during heavy ion irradiation and the subsequent damage accumulation and recovery in InP is far from being completely understood. In terms of the damage accumulation mechanisms, the conclusions drawn in the numerous studies performed have often been in conflict with one another. A factor contributing to the uncertainties associated with these conflicting results is a lack of information and direct observation of the “building blocks” leading to the ultimate damage created at high ion fluences as an amorphous layer. These building blocks formed at lower fluence regimes by single ion impacts can be directly observed as isolated disordered zones and ion tracks for low energy and swift heavy ion irradiation, respectively. ¶ The primary aim of this work has thus been to obtain a better understanding of the disorder in this material through direct observations and investigation of disorder produced by individual heavy ions in both energy regimes (i.e. elastic and inelastic energy deposition regimes) especially with low ion fluence irradiations. In this thesis the heavy ion induced disorder introduced by low energy Au ions (100 keV Au+) and high energy Au (200 MeV Au+16) ion irradiation in InP were investigated using Transmission Electron Microscopy (TEM), Rutherford Backscattering Spectrometry (RBS/C) and Atomic Force Microscopy (AFM). ¶ ...

The interaction of swift heavy ions (SHIs) with solids is characterised by inelastic collisions between the ions and the target electrons. SHIs typically deposit tens of keV/nm of energy in the target material causing extreme excitation of the electronic subsystem that result in different damage formation mechanisms than for ion implantation such as the formation of ion tracks, plastic deformation or porous layer formation. The crystalline phases of the elemental semiconductors Ge and Si are relatively resistant to SHI irradiation induced damage. In contrast, their amorphous counterparts (a-Ge and a-Si, respectively) are subject to SHI irradiation induced plastic deformation and porous layer formation. The former is caused by ion hammering and entirely predicated on the creation of ion tracks and thus provides indirect evidence for ion-track formation in a-Ge and a-Si. SHI irradiation was performed on a-Ge, a-Si and amorphous Si(1-x)Ge(x) (a-Si(1-x)Ge(x)) with different stoichiometries to study the study ion-track and porous layer formation in these materials. Synchrotron-based small-angle x-ray scattering was utilised to characterise the structure of ion tracks in the amorphous materials and the formation of nanoporosity was investigated by scanning electron microscopy. The experimental observations were complemented by a novel theoretical approach comprising a Monte Carlo calculation of the electron dynamics, a Two-Temperature Model description of the heat dissipation, and Molecular Dynamics simulations of the atom dynamics. Ion-track formation has been identified for a-Ge, a-Si and a-Si(1-x)Ge(x) alloys. While SHI irradiation of all such materials results in the formation of overall densified ion tracks with an underlying core-shell morphology, different mechanisms for the formation of ion tracks are revealed. Ion tracks in a-Ge are comprised of an under-dense shell surrounded by an over-dense core. The formation of ion-tracks is accompanied by the formation of non-spherical voids which are identified as the precursors for the porous layer formation under continuing SHI irradiation. On the contrary, ion tracks in a-Si and a-Si(1-x)Ge(x) alloys feature a dominant over-dense core surrounded by an under-dense shell. The formation of non-spherical voids was observed for a-Si(0.2)Ge(0.8), however, voids are absent in all other SHI irradiated alloys and a-Si. Continuous SHI irradiation leads to the formation of porosity in a-Ge, a-Si and a-Si(1-x)Ge(x) alloys. In a-Ge and Ge-rich a-Si(1-x)Ge(x) alloys, self-organisation of pores into well separated porous layers occurs. The layering effect depends on the irradiation energy, angle of incidence and thickness of the amorphous layer. SHI irradiation induced void formation in a-Si occurs at much higher ion fluences relative to a-Ge. In contrast to a-Ge, no self-organisation of pores is apparent in a-Si and the voids exhibit a cavity-like morphology, which implies a different void formation mechanism in the two elemental semiconductors. The results on ion-track and porous layer formation in a-Ge, a-Si and a-Si(1-x)Ge(x) alloys shed new light on the damage evolution in amorphous semiconductors due to high electronic excitation and may provide a pathway for the development of novel materials.

This work provides a systematic study of ion irradiation to tailor the physical and chemical properties of a-SiO2, a-Si3N4 and a-SiOxNy materials with a particular focus on three specific areas: (i) the formation of ion tracks by swift heavy-ion (SHI) irradiation in a-SiO2, a-Si3N4, and a-SiOxNy, (ii) the ion beam synthesis of Au nanoparticles (NPs) in a-SiO2 and a-Si3N4; and (iii) the ion shaping process of embedded metallic NPs in a-Si2, a-Si3N4 and at their interface. (i) Ion tracks were created by SHI irradiation of a-SiO2, a-Si3N4 and a-SiOxNy of different composition, with 185 MeV and 2.2 GeV Au ions at fluences between 1 x 10^11 - 1 x 10^13 cm^-2. Small-angle X-ray scattering (SAXS) revealed a cylindrical ion track morphology which resembles, for all materials and compositions considered, an under-dense core surrounded by an over-dense shell with a smooth transition between the two regions, in good agreement with molecular-dynamics simulations. A decrease in the ion track dimensions for samples with higher nitrogen content was determined, accompanied by an increased density change. The latter is attributed to the short-lived thermal spike resulting from the higher thermal conductivity associated with a-Si3N4. IR spectroscopy analysis shows a region of high radiation damage region within the ion track core for a-SiO2 and a-Si3N4. (ii) To study the synthesis of metallic NPs, a-SiO2 and a-Si3N4 were implanted with 2 MeV Au ions at a fluence of 5 x 10^16 cm^-2. The synthesis and growth was promoted by thermal annealing for 60 minutes in either air or N2 gas at temperatures between 1000 and 1100 C. Characterization with SAXS and transmission electron microscopy (TEM) of a-SiO2 showed that the Au NP growth rate exhibits very little difference between thermally grown and plasma enhanced chemical vapour deposited (PECVD) thin layers. In the case of a-Si3N4, when deposited by PECVD the NP growth is very limited, accompanied by the formation of voids at the depth of maximum implantation damage and the formation of NPs with a mean diameter of 3 nm while the a-Si3N4 layer remains amorphous. FTIR showed the presence of Si-H absorbance bands after annealing suggesting a high thermal stability. When the a-Si3N4 layer is deposited by low pressure CVD (LPCVD), the layer undergoes an amorphous-to-poly-crystalline phase transformation. For the study of the ion shaping process of Au NPs embedded in a-SiO2, a-Si3N4 and at the interface of a-SiO2 and a-Si3N4 a good control of the initial NPs size is required. To achieve that, Au NPs were synthesised by depositing two layers of a-SiO2 (or a-Si3N4) of few hundred nanometres in thickness with a 5 nm thick Au layer in-between, followed by subsequent rapid thermal annealing (RTA). (iii) The ion-irradiation induced elongation of embedded Au NPs was carried out by SHI irradiation with 185 MeV Au ions. Transmission electron microscopy (TEM) revealed different elongation rates in a-SiO2 and a-Si3N4. For the former, an evolution from sphere to rod-like NPs with increasing fluence was observed, while for the latter, the Au NPs evolved towards faceted prolate NPs with smaller aspect ratios. When NPs are located at the interface between a-SiO2 and a-Si3N4, preferential elongation towards the a-SiO2 layer was observed with a limited elongation towards the a-Si3N4 layer. Numerical simulations based on the three-dimensional thermal spike (3D-TS) model showed, in the single layer case, a thermal spike duration of about 20 and 10 ps for a-SiO2 and a-Si3N4, respectively. The shorter lifetime and the thermal profile calculated for a-Si3N4 agree with the reduced efficiency of the elongation process observed. In the case of Au NPs located at the interface, the preferential diffusion of Au towards the ion track formed in a-SiO2 can also be explained by the difference of the thermal spike life-time between the two materials, and the reduced efficiency of the elongation process in a-Si3N4.

Die Bestrahlung von tetraedrisch amorphen Kohlenstoff (ta-C) mit schnellen schweren Ionen führt zur Bildung von mikroskopischen elektrisch leitfähigen Ionenspuren mit Durchmessern um 10 nm. Dieses Phänomen ist auf das sp² zu sp³ Hybridisierungsverhältnis des amorphen Kohlenstoffes zurückzuführen. Das einschlagende Ion deponiert eine große Menge Energie innerhalb des Spurvolumens, so dass eine Materialtransformation hin zu höheren sp² Hybridisierung stattfindet. Hierdurch wird die elektrische Leitfähigkeit der Ionenspur stark erhöht. Dieser Effekt kann durch die Zugabe von Verunreinigungen wie Kupfer verstärkt werden. Das Ziel dieser Arbeit ist die umfassende Analyse des elektrischen Verhaltens von ta-C mit besonderen Augenmerk auf die Auswirkungen von Kupferverunreinigungen und Ionenspuren. Der Effekt von Kupferverunreinigungen auf das wichtige Hybridisierungsverhältnis vom amorphen Kohlenstoff wird vermessen. Darüber hinaus wurden alle Proben elektrisch mit makroskopischen Kontakten im Temperaturbeireich von 20 K bis 380 K analysiert. Mikroskopisch wurden einzelne leitfähige Ionenspuren mit Hilfe von atomarer Kraftmikroskopie betrachtet. Die statistische Verteilung der Spureigenschaften in Kohlenstofffilmen mit verschiedenen Kupferkonzentrationen werden verglichen, um die Spurbildung besser zu verstehen. Die normalisierten durchschnittlichen Spurleitfähigkeiten aus mikroskopischen und makroskopischen Messungen werden verglichen. Hierbei kann die Zuverlässigkeit der beiden experimentellen Methoden bewertet werden und mögliche Fehlerquellen ausfindig gemacht werden. Schließlich wird ein Konzept für eine Anwendung unterbrochener Ionenspuren gezeigt.