Focused Ion Beam (FIB) technology is a versatile tool that can be applied in many fields to great effect, including semiconductor device prototyping, Transmission Electron Microscopy (TEM) sample preparation, and nanoscale tomography. Developments in FIB technology, including the availability of alternative ion sources and improvements in automation capacity, make FIB an increasingly attractive option for many tasks. In this thesis, FIB systems are applied to photonic device fabrication and modification, semiconductor reverse engineering, and the production of structures for the study of nanoscale radiative heat transfer. Optical facets on silicon nitride waveguides were produced with plasma FIB (PFIB) and showed an improvement of 3 ± 0.9 dB over reactive ion etched (RIE) facets. This process was then automated and is capable of producing a facet every 30 seconds with minimal oversight. PFIB was then employed to develop a method for achieving local backside circuit access for circuit editing, creating local trenches with flat bases of 200 x 200 μm. Gas assisted etching using xenon difluoride was then used in order to accelerate the etch process. Finally, several varieties of nanogap structure were fabricated on devices capable of sustaining temperature gradients, achieving a minimum gap size with PFIB of 60 nm. / Thesis / Master of Applied Science (MASc)

In the present investigation, a comprehensive photonic characterization and analysis of low energy Ar⁺ ion beam processed GaAs surfaces is presented. The purpose of this investigation was to evaluate the damage and amorphization introduced at the surface and sub-surface regions by ion bombardment. Ar⁺ ion beam etching was selected in order to rule out the possibility of producing any additional effects at the interface due to chemical reactions in the case of reactive ion etching. After a brief review of the concepts and underlying physics, several photonic structures are introduced. The basic theory governing the photovoltaic devices and photoconductive samples is discussed. The preparation and characterization techniques of ion beam processed GaAs samples are described. An automated photovoltaic materials and devices (PVMD) system was developed. Asyst, a Forth based scientific software was selected to write the source codes for data acquisition and reduction. The inherent fast execution times of the software allows data acquisition in real time, ensuring the quasi-steady state condition. The electrical and optical evaluation procedures developed and employed for the present investigation are discussed. One of the striking features of the ion beam bombardment on semi-insulating (SI) GaAs samples was the observation of persistent photoconductivity. A phenomenological model for optically generated ion beam induced metastable defect state formation was proposed to explain the persistent photoconductivity. Presence of two or more exponential curves in the relaxation mode indicates the distributed nature of the traps within the band gap. A conjectural flat-band energy diagram was introduced to elucidate the proposed model. The observed dark and photoconductivity response model was based on the distributed lumped electrical components analysis. Fundamental transport equations were employed in the analysis of the lumped electrical components model. Metal-Insulator-Semiconductor (MIS) type Schottky barrier diodes and photodiodes were fabricated employing both thermal and anodic oxides. Diode parameters were evaluated as a function of ion-beam energy. An increase in reverse saturation current density accompanied by an increase in the ideality factor was observed, indicating the presence of trap-assisted tunneling and a region of high recombination. The effective barrier height was generally lowered; however, no monotonic correlation with the ion energy was observed. It is proposed that the mechanisms described in previous studies (e.g. tunneling, stoichiometry effects, ion penetration depth) were dominated by the effect of Fermi level pinning at the electronic states of process-induced defects. Deep level transient spectroscopy (DLTS) indicated the presence of at least two distinct deep trap levels, at 0.32 eV and at 0.52 eV below the conduction band edge, as a consequence of ion beam etching. The EL2 peak was evident in the virgin sample and vanished in the ion beam etched samples and such observation is in agreement with our proposed model. The photovoltaic response was characterized using illuminated current-voltage (I-V) and spectral response measurements. The ratio of external quantum efficiencies of IBE devices to unetched device indicates the regions and relative extent of the damage. Since the damage has a impact on the band-bending due to excess carrier generation, the sub-bandgap photon absorption response reveals the degree of disorder. XPS results indicated an increased surface sensitivity and change in Ga/As ratio as a function of ion beam energy. The modelling of ion-beam-processed samples was considered and several computer programs which simulate their operation are described. The depth of amorphization was calculated using the Lindhard-Scharff-SchiΦtt (LSS) theory and the standard projected range and straggle parameters, and experimental parameters. A large difference was observed in the values calculated using LSS theory and experimentally measured values, using optical probes. The difference was explained in light of the Collision-Cascade model. / Ph. D.

Anodic aluminum oxide (AAO) nanopores are excellent templates to fabricate different nanostructures. However, the pores are limited to a hexagonal arrangement with a domain size of a few micrometers.  In this dissertation, focused ion beam (FIB) is used to create pre-patterned concaves to guide the anodization. Due to the advantage of FIB lithography, highly ordered AAO arrays with different arrangements, alternating diameters, and periodic pore densities are successfully achieved. Anodization window to fabricate ordered AAO is enlarged due to the FIB pre-pattern guidance. AAO has also been successfully used as a template to nanoimprint prepolymer to synthesize vertically aligned and high aspect ratio h-PDMS nanorod arrays with Moiré pattern arrangements. The formation mechanism of anodic TiO2 nanotubes is proposed in this dissertation. Moreover, FIB pre-pattern guided anodization is introduced to synthesize highly ordered TiO₂ nanotubes with different morphologies. The effects of inter-tube distance and arrangement to the structure of TiO₂ nanotubes are investigated. TiO2 nanotubes with branched and bamboo-type structures are achieved by adjusting anodization voltage. The influence of patterned concave depth and surface curvature on the growth of TiO₂ nanotubes and AAO are studied. The efficiency of TiO₂ nanotubes in supercapacitors and photoelectrochemical water splitting are optimized by enlarging surface area and increasing electrical conductivity. Focused ion beam can not only create concave arrays to guide the electrochemical anodization, but also be used for nanoscale sculpting and 3D analysis. When the TiO₂ nanotube surface is bombarded by FIB, there is a mass transfers due to ion-induced viscous flow and sputter milling, thus the TiO₂ nanotubes are selectively closed and opened. By combining FIB cutting and SEM imaging to create a series of 2D cross section SEM images, 3D reconstruction can be obtained by stacking SEM images together. This 3D reconstruction offers an opportunity to directly and quantitatively observe the pore evolution to understand the sintering process. / Ph. D.

Anodization is a kind of method that can produce oxide layer in a large area and on flexible shaped metals. In some specific conditions, anodic oxide layers exhibit interesting nanopore/nanotube structures. In this work, focused ion beam patterning method is introduced to general anodization, aiming to make highly ordered anodic porous alumina and titania nanotubes. Focused ion beam guided porous anodic alumina is carried out by pre-designing hexagonal and square guiding patterns with different interpore distances on well electropolished Al foil before anodization. After anodization, the guiding interpore distance is found to affect the new pores' locations and shapes. Two important elements, electrical field and mechanical stress, are discussed for the development of the guiding pores and the generation of new pores. Based on the proposed pore growth mechanism, novel patterns, non-spherical pores, and large patterns across the grain boundaries are successfully produced. The research on focused ion beam guided anodic titania nanotubes begins with surface polishing. The influence of four polishing conditions, as-received, chemically polished, mechanically polished, and electropolished samples, are investigated. A polished smooth sample provides a desired surface for focused ion beam guided anodization. Hexagonal guiding patterns with different interpore distances are created on Ti surface. Ordered nanotube arrays are produced, and the structure of the anodized guiding pattern is identified. / Master of Science

abstract: Water affinity and condensation on Si-based surfaces is investigated to address the problem of fogging on silicone intraocular lenses (IOL) during cataract surgery, using Si(100), silica (SiO2) and polydimethylsiloxane (PDMS) silicone (SiOC2H6)n. Condensation is described by two step nucleation and growth where roughness controls heterogeneous nucleation of droplets followed by Ostwald ripening. Wetting on hydrophilic surfaces consists of continuous aqueous films while hydrophobic surfaces exhibit fogging with discrete droplets. Si-based surfaces with wavelength above 200 nm exhibit fogging during condensation. Below 200 nm, surfaces are found to wet during condensation. Water affinity of Si-based surfaces is quantified via the surface free energy (SFE) using Sessile drop contact angle analysis, the Young-Dupré equation, and Van Oss theory. Topography is analyzed using tapping mode atomic force microscopy (TMAFM). Polymer adsorption and ion beam modification of materials (IBMM) can modify surface topography, composition, and SFE, and alter water affinity of the Si-based surfaces we studied. Wet adsorption of hydroxypropyl methylcellulose (HPMC) C32H60O19 with areal densities ranging from 1018 atom/cm2 to 1019 atom/cm2 characterized via Rutherford backscattering spectrometry (RBS), allows for the substrate to adopt the topography of the HPMC film and its hydrophilic properties. The HPMC surface composition maintains a bulk stoichiometric ratio as confirmed by 4.265 MeV 12C(α, α)12C and 3.045 MeV 16O(α, α)16O, and 2.8 MeV He++ elastic recoil detection (ERD) of hydrogen. Both PIXE and RBS methods give comparable areal density results of polymer films on Si(100), silica, and PDMS silicone substrates. The SFE and topography of PDMS silicone polymers used for IOLs can also be modified by IBMM. IBMM of HPMC cellulose occurs during IBA as well. Damage curves and ERD are shown to characterize surface desorption accurately during IBMM so that ion beam damage can be accounted for during analysis of polymer areal density and composition. IBMM of Si(100)-SiO2 ordered interfaces also induces changes of SFE, as ions disorder surface atoms. The SFE converges for all surfaces, hydrophobic and hydrophilic, as ions alter electrochemical properties of the surface via atomic and electronic displacements. / Dissertation/Thesis / Ph.D. Physics 2011

Doctor of Philosophy / Department of Physics / Itzhak Ben-Itzhak / Present advances in laser technology allow the production of ultrashort (≲5 fs, approaching single cycle at 800 nm), intense tabletop laser pulses. At these high intensities laser-matter interactions cannot be described with perturbation theory since multiphoton processes are involved. This is in contrast to photodissociation by the absorption of a single photon, which is well described by perturbation theory. For example, at high intensities (≳5×10[superscript]13 W/cm[superscript]2) the fragmentation of molecular hydrogen ions has been observed via the absorption of three or more photons. In another example, an intriguing dissociation mechanism has been observed where molecular hydrogen ions seem to fragment by apparently absorbing no photons. This is actually a two photon process, photoabsorption followed by stimulated emission, resulting in low energy fragments. We are interested in exploring these kinds of multiphoton processes. Our research group has studied the dynamics and control of fragmentation induced by strong laser fields in a variety of molecular targets. The main goal is to provide a basic understanding of fragmentation mechanisms and possible control schemes of benchmark systems such as H[subscript]2[superscript]+. This knowledge is further extended to more complex systems like the benchmark H[subscript]3[superscript]+ polyatomic and other molecules. In this dissertation, we report research based on two types of experiments. In the first part, we describe laser-induced fragmentation of molecular ion-beam targets. In the latter part, we discuss the formation of highly-excited neutral fragments from hydrogen molecules using ultrashort laser pulses. In carrying out these experiments, we have also extended experimental techniques beyond their previous capabilities. We have performed a few experiments to advance our understanding of laser-induced fragmentation of molecular-ion beams. For instance, we explored vibrationally resolved spectra of O[subscript]2[superscript]+ dissociation using various wavelengths. We observed a vibrational suppression effect in the dissociation spectra due to the small magnitude of the dipole transition moment, which depends on the photon energy --- a phenomenon known as Cooper minima. By changing the laser wavelength, the Cooper minima shift, a fact that was used to identify the dissociation pathways. In another project, we studied the carrier-envelope phase (CEP) dependences of highly-excited fragments from hydrogen molecules. General CEP theory predicts a CEP dependence in the total dissociation yield due to the interference of dissociation pathways differing by an even net number of photons, and our measurements are consistent with this prediction. Moreover, we were able to extract the difference in the net number of photons involved in the interfering pathways by using a Fourier analysis. In terms of our experimental method, we have implemented a pump-probe style technique on a thin molecular ion-beam target and explored the feasibility of such experiments. The results presented in this work should lead to a better understanding of the dynamics and control in molecular fragmentation induced by intense laser fields.

Heavy Ion Elastic Recoil Detection Analysis (HIERDA) is a versatile Ion Beam Analysis technique well suited to multi-elemental depth profiling of thin layered structures and near-surface regions of materials. An existing limitation is the inability to accurately account for the pronounced broadening and tailing effects of multiple scattering typically seen in HIERDA spectra. This thesis investigates the role of multiple large angle scattering in heavy ion applications such as HIERDA, and seeks to quantify its contribution to experimental output. This is achieved primarily by the development of a computer simulation capable of predicting these contributions and using it to classify and quantify the interactions that cause them. Monte Carlo ion transport simulation is used to generate simulated HIERDA spectra and the results are compared to experimental data acquired using the Time of Flight HIERDA facility at the Australian Nuclear Science and Technology Organisat ion. A Monte Carlo simulation code was adapted to the simulation of HIERDA spectra with considerable attention on improving the modelling efficiency to reduce processing time. Efficiency enhancements have achieved simulation time reductions of two to three orders of magnitude. The simulation is shown to satisfactorily reproduce the complex shape of HIERDA spectra. Some limitations are identified in the ability to accurately predict peak widths and the absolute magnitude of low energy tailing in some cases. The code is used to identify the plural scattering contribution to the spectral features under investigation, and the complexity of plurally scattered ion and recoil paths is demonstrated. The program is also shown to be useful in the interpretation of overlapped energy spectra of elements of similar mass whose signals cannot be reliably separated experimentally. The effect of large angle scattering on the transmission of heavy ions through a nano-scale aperture mask, used to collimate an ion beam to a very small beam spot, is modelled using a version of the program adapted to handle the more complex geometry of the aperture mask. The effectiveness of nano-aperture collimation was studied for a variety of ion-energy combinations. Intensity, energy, and angular distributions of transmitted ions were calculated to quantify the degree to which scattering within the mask limits the spatial resolution achievable. The simulation successfully predicted the effect of misaligning the aperture and the beam, and the result has subsequently been observed experimentally. Transmitted ion distributions showed that the higher energy heavier ions studied are more effectively collimated than are lower energy lighter ions. However, there is still a significant probability of transmission of heavy ions with substantial residual energy beyond the perimeter of the aperture. For the intended application, ion beam lithography, these ions are likely to be problematic. The results indicate that medium energy He ions are the more attractive option, as the residual energy of scattered transmitted ions can be more readily managed by customising the etching process. Continuing research by experimentalists working in this area is proceeding in this direction as a result of the conclusions from this work.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and about 1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain "magic" angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and about 1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain "magic" angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.:1 Introduction: Atomistic Models 1 1.1 Density Functional Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.1.1 Schroedinger equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.1.2 Density functional theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 1.2 Molecular Dynamics Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 1.2.1 Lagrangian mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.2.2 MD algorithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.3 Lattice Monte Carlo simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 1.3.1 Thermodynamic variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 1.3.2 Metropolis Algorithm and limit theorem . . . . . . . . . . . . . . . . . . . . . 15 1.3.3 Kinetic Monte Carlo Simulation . . . . . . . . . . . . . . . . . . . . . . . . . 18 1.3.4 Imaginary time reaction diffusion . . . . . . . . . . . . . . . . . . . . . . . . . 24 2 Cluster Growth on Pre-patterned Surfaces 29 2.1 Nanocluster growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.1.1 Classical nucleation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.1.2 Cluster growth on substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.1.3 Experimental motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 2.2 Local flux and surface ad-monomer diffusion . . . . . . . . . . . . . . . . . . . . . . 35 2.2.1 Surface topography and local flux . . . . . . . . . . . . . . . . . . . . . . . . 35 2.2.2 Surface gas diffusion under inhomogeneous flux . . . . . . . . . . . . . . . . . 37 2.2.3 Surface migration of ad-monomers . . . . . . . . . . . . . . . . . . . . . . . . 40 2.2.4 Simulation vs. experimental gauge . . . . . . . . . . . . . . . . . . . . . . . . 45 2.3 Nucleation models: Surface gas condensation . . . . . . . . . . . . . . . . . . . . . . 46 2.3.1 Simulation setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 2.3.2 Simulation parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.3.3 Evolution of sticking probability . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.3.4 Evolution of Ag cluster growth . . . . . . . . . . . . . . . . . . . . . . . . . . 54 2.3.5 Simulation time and system evolution . . . . . . . . . . . . . . . . . . . . . . 57 2.4 Extended cluster growth model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 2.4.1 Modified setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 2.4.2 Simulation result . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 2.4.3 Comparison with experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3 A Markov chain model of transition states 63 3.1 Acceleration of thin film growth simulation . . . . . . . . . . . . . . . . . . . . . . . 63 3.2 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 3.3 Transition states of Markov chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.3.1 Local transition events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.3.2 The Monte-Carlo method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.4 Effective transitions of objects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3.4.1 Convergence of the local fluctuation . . . . . . . . . . . . . . . . . . . . . . . 67 3.4.2 The importance of individual local transitions . . . . . . . . . . . . . . . . . . 68 3.4.3 The modified algorithm for effective transition states . . . . . . . . . . . . . . 69 3.5 Cluster growth simulation models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 3.5.1 The configuration energy and migration barriers . . . . . . . . . . . . . . . . 72 3.5.2 Transition events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 3.5.3 Comparison with Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.5.4 Cluster growth stability evaluation . . . . . . . . . . . . . . . . . . . . . . . . 78 3.6 Stability of modified convergence limit . . . . . . . . . . . . . . . . . . . . . . . . . . 80 3.6.1 Acceleration of convergence to Gibbs field . . . . . . . . . . . . . . . . . . . . 80 3.6.2 Relative convergence speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 3.6.3 1D Ag models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.6.4 Stability theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 3.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 4 Ion beam inducing surface pattern formation 89 4.1 Ion-inducing pattern formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 4.1.1 Bradley-Harper equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 4.1.2 Nonlinear continuum models . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 4.1.3 Other approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.2 Simulation of surface defects induced by ion beams . . . . . . . . . . . . . . . . . . . 94 4.2.1 MD simulation of single ion impact . . . . . . . . . . . . . . . . . . . . . . . . 94 4.2.2 Monte-Carlo simulations of surface modification . . . . . . . . . . . . . . . . 96 4.2.3 Curvature dependent surface diffusion . . . . . . . . . . . . . . . . . . . . . . 102 4.3 Continuum model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 4.3.1 Equation of motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 4.3.2 A travelling wave solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 4.3.3 Lyapunov stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 4.3.4 Comparison with experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 4.3.5 Approximate solutions for other angles . . . . . . . . . . . . . . . . . . . . . . 110 4.4 Contribution of other effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 4.4.1 Surface diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 4.4.2 Surface Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 4.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 5 Summary 119 Appendix 123 A The discrete reaction diffusion equation . . . . . . . . . . . . . . . . . . . . . . . . . 123 B The derivation of the solution (2.20) . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 C Contribution of overlapping migration area . . . . . . . . . . . . . . . . . . . . . . . 125 D The RGL potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 E Stability of the traveling wave solution . . . . . . . . . . . . . . . . . . . . . . . . . . 127

Yes / A novel process chain for serial production of polymer-based devices incorporating both micro- and nano-scale features is proposed. The process chain is enabled by the use of Zr-based bulk metallic glasses (BMG) to achieve the necessary level of compatibility and complementarity between its component technologies. It integrates two different technologies, namely laser ablation and focused ion beam (FIB) milling for micro-structuring and sub-micron patterning, respectively, thus to fabricate inserts incorporating different length scale functional features. Two alternative laser sources, namely nano-second (NS) and pico-second (PS) lasers, were considered as potential candidates for the first step in this master-making process chain. The capabilities of the component technologies together with some issues associated with their integration were studied. To validate the replication performance of the produced masters, a Zr-based BMG insert was used to produce a small batch of micro-fluidic devices by micro-injection moulding. Furthermore, an experimental study was also carried out to determine whether it would be possible by NS laser ablation to structure the Zr-based BMG workpieces with a high surface integrity whilst retaining the BMG's non-crystalline morphology. Collectively, it was demonstrated that the proposed process chain could be a viable fabrication route for mass production of polymer devices incorporating different length scale features.