Growth and Modification of Cluster-Assembled Thin Films

Thin film applications have become increasingly important in our search for multifunctional and economically viable technological solutions of the future. Thin film coatings can be used for a multitude of purposes, ranging from a basic enhancement of aesthetic attributes to the addition of a complex surface functionality. Anything from electronic or optical properties, to an increased catalytic or biological activity, can be added or enhanced by the deposition of a thin film, with a thickness of only a few atomic layers at the best, on an already existing surface. Thin films offer both a means of saving in materials and the possibility for improving properties without a critical enlargement of devices. Nanocluster deposition is a promising new method for the growth of structured thin films. Nanoclusters are small aggregates of atoms or molecules, ranging in sizes from only a few nanometers up to several hundreds of nanometers in diameter. Due to their large surface to volume ratio, and the confinement of atoms and electrons in all three dimensions, nanoclusters exhibit a wide variety of exotic properties that differ notably from those of both single atoms and bulk materials. Nanoclusters are a completely new type of building block for thin film deposition. As preformed entities, clusters provide a new means of tailoring the properties of thin films before their growth, simply by changing the size or composition of the clusters that are to be deposited. Contrary to contemporary methods of thin film growth, which mainly rely on the deposition of single atoms, cluster deposition also allows for a more precise assembly of thin films, as the configuration of single atoms with respect to each other is already predetermined in clusters. Nanocluster deposition offers a possibility for the coating of virtually any material with a nanostructured thin film, and therein the enhancement of already existing physical or chemical properties, or the addition of some exciting new feature. A clearer understanding of cluster-surface interactions, and the growth of thin films by cluster deposition, must, however, be achieved, if clusters are to be successfully used in thin film technologies. Using a combination of experimental techniques and molecular dynamics simulations, both the deposition of nanoclusters, and the growth and modification of cluster-assembled thin films, are studied in this thesis. Emphasis is laid on an understanding of the interaction between metal clusters and surfaces, and therein the behaviour of these clusters during deposition and thin film growth. The behaviour of single metal clusters, as they impact on clean metal surfaces, is analysed in detail, from which it is shown that there exists a cluster size and deposition energy dependent limit, below which epitaxial alignment occurs. If larger clusters are deposited at low energies, or cluster-surface interactions are weaker, non-epitaxial deposition will take place, resulting in the formation of nanocrystalline structures. The effect of cluster size and deposition energy on the morphology of cluster-assembled thin films is also determined, from which it is shown that nanocrystalline cluster-assembled films will be porous. Modification of these thin films, with the purpose of enhancing their mechanical properties and durability, without destroying their nanostructure, is presented. Irradiation with heavy ions is introduced as a feasible method for increasing the density, and therein the mechanical stability, of cluster-assembled thin films, without critically destroying their nanocrystalline properties. The results of this thesis demonstrate that nanocluster deposition is a suitable technique for the growth of nanostructured thin films. The interactions between nanoclusters and their supporting surfaces must, however, be carefully considered, if a controlled growth of cluster-assembled thin films, with precisely tailored properties, is to be achieved.

Dynamic and thermodynamic anomalies of water at low temperatures: from bulk water to reverse micelles and DNA hydration layer

Liquid water is known to exhibit remarkable thermodynamic and dynamic anomalies, ranging from solvation properties in supercritical state to an apparent divergence of the linear response functions at a low temperature. Anomalies in various dynamic properties of water have also been observed in the hydration layer of proteins, DNA grooves and inside the nanocavity, such as reverse micelles and nanotubes. Here we report studies on the molecular origin of these anomalies in supercooled water, in the grooves of DNA double helix and reverse micelles. The anomalies have been discussed in terms of growing correlation length and intermittent population fluctuation of 4- and 5-coordinated species. We establish correlation between thermodynamic response functions and mean squared species number fluctuation. Lifetime analysis of 4- and 5-coordinated species reveals interesting differences between the role of the two species in supercooled and constrained water. The nature and manifestations of the apparent and much discussed liquid-liquid transition under confinement are found to be markedly different from that in the bulk. We find an interesting `faster than bulk' relaxation in reverse micelles which we attribute to frustration effects created by competition between the correlations imposed by surface interactions and that imposed by hydrogen bond network of water.

Nanostructure of giant magnetoresistive oxide film Nd2/3Sr1/3MnO3 by scanning tunneling microscopy

Scanning tunneling microscopy was used to study the surface nanostructure of the epitaxial film Nd2/3Sr1/3MnO3 that shows giant magnetoresistance. The surface morphology of the film consists of a number of overlapping platelets of about 30–35 Å diameter that grow at an angle of 35°–45° to the surface normal. The peak to peak height of the platelets are multiples of the c‐axis lattice parameter of 7.85 Å showing that the growth of the platelets takes place by the layer by layer addition of one formula unit. The mean surface roughness is about 10 Å. In the range of a few microns the film exhibits no defects or dislocations. The film is unstable in ambient atmosphere and tends to get covered by an adsorbate layer. Tip‐surface interactions cause the adsorbate to be dislodged exposing the surface nanostructure. The degradation of the film in real time when imaged in air was recorded. The adsorbates increase the surface roughness of the film.

Virus-sized colloid transport in a single pore: Model development and sensitivity analysis

A mathematical model is developed to simulate the transport and deposition of virus-sized colloids in a cylindrical pore throat considering various processes such as advection, diffusion, colloid-collector surface interactions and hydrodynamic wall effects. The pore space is divided into three different regions, namely, bulk, diffusion and potential regions, based on the dominant processes acting in each of these regions. In the bulk region, colloid transport is governed by advection and diffusion whereas in the diffusion region, colloid mobility due to diffusion is retarded by hydrodynamic wall effects. Colloid-collector interaction forces dominate the transport in the potential region where colloid deposition occurs. The governing equations are non-dimensionalized and solved numerically. A sensitivity analysis indicates that the virus-sized colloid transport and deposition is significantly affected by various pore-scale parameters such as the surface potentials on colloid and collector, ionic strength of the solution, flow velocity, pore size and colloid size. The adsorbed concentration and hence, the favorability of the surface for adsorption increases with: (i) decreasing magnitude and ratio of surface potentials on colloid and collector, (ii) increasing ionic strength and (iii) increasing pore radius. The adsorbed concentration increases with increasing Pe, reaching a maximum value at Pe = 0.1 and then decreases thereafter. Also, the colloid size significantly affects particle deposition with the adsorbed concentration increasing with increasing particle radius, reaching a maximum value at a particle radius of 100 nm and then decreasing with increasing radius. System hydrodynamics is found to have a greater effect on larger particles than on smaller ones. The secondary minimum contribution to particle deposition has been found to increase as the favorability of the surface for adsorption decreases. The sensitivity of the model to a given parameter will be high if the conditions are favorable for adsorption. The results agree qualitatively with the column-scale experimental observations available in the literature. The current model forms the building block in upscaling colloid transport from pore scale to Darcy scale using Pore-Network Modeling. (C) 2014 Elsevier By. All rights reserved.

Shocked Flows Induced by Supersonic Projectiles Moving in Tubes

A numerical study on shocked flows induced by a supersonic projectile moving in tubes is described in this paper. The dispersion-controlled scheme was adopted to solve the Euler equations implemented with moving boundary conditions. Four test cases were carried out in the present study: the first two cases are for validation of numerical algorithms and verification of moving boundary conditions, and the last two cases are for investigation into wave dynamic processes induced by the projectile moving at Mach numbers of M-p = 2.0 and 2.4, respectively, in a short time duration after the projectile was released from a shock tube into a big chamber. It was found that complex shock phenomena exist in the shocked flow, resulting from shock-wave/projectile interaction, shock-wave focusing, shock-wave reflection and shock-wave/contact-surface interactions, from which turbulence and vortices may be generated. This is a fundamental study on complex shock phenomena, and is also a useful investigation for understanding on shocked flows in the ram accelerator that may provide a highly efficient facility for launching hypersonic projectiles.

Transitions Between Different Contact Models

The transitions between the different contact models which include the Hertz, Bradley, Johnson-Kendall-Roberts (JKR), Derjaguin-Muller-Toporov (DMT) and Maugis-Dugdale (MD) models are revealed by analyzing their contact pressure profiles and surface interactions. Inside the contact area, surface interaction/adhesion induces tensile contact pressure around the contact edge. Outside the contact area, whether or not to consider the surface interaction has a significant influence on the contact system equilibrium. The difference in contact pressure due to the surface interaction inside the contact area and the equilibrium influenced by the surface interaction outside the contact area are physically responsible for the different results of the different models. A systematic study on the transitions between different models is shown by analyzing the contact pressure profiles and the surface interactions both inside and outside the contact area. The definitions of contact radius and the flatness of contact surfaces are also discussed. (C) Koninklijke Brill NV, Leiden, 2008.

Altering the ordering and disordering of a triangular nanographene at room temperature.

Molecular self-organization has the potential to serve as an efficient and versatile tool for the spontaneous creation of low-dimensional nanostructures on surfaces. We demonstrate how the subtle balance between intermolecular interactions and molecule-surface interactions can be altered by modifying the environment or through manipulation by means of the tip in a scanning tunnelling microscope (STM) at room temperature. We show how this leads to the distinctive ordering and disordering of a triangular nanographene molecule, the trizigzag-hexa-peri-hexabenzocoronenes-phenyl-6 (trizigzagHBC-Ph6), on two different surfaces: graphite and Au(111). The assembly of submonolayer films on graphite reveals a sixfold packing symmetry under UHV conditions, whereas at the graphite-phenyloctane interface, they reorganize into a fourfold packing symmetry, mediated by the solvent molecules. On Au(111) under UHV conditions in the multilayer films we investigated, although disorder prevails with the molecules being randomly distributed, their packing behaviour can be altered by the scanning motion of the tip. The asymmetric diode-like current-voltage characteristics of the molecules are retained when deposited on both substrates. This paper highlights the importance of the surrounding medium and any external stimulus in influencing the molecular organization process, and offers a unique approach for controlling the assembly of molecules at a desired location on a substrate.

Photoconductive hybrid films via directional self-assembly of C 60 on aligned carbon nanotubes

Hybrid nanostructured materials can exhibit different properties than their constituent components, and can enable decoupled engineering of energy conversion and transport functions. Novel means of building hybrid assemblies of crystalline C 60 and carbon nanotubes (CNTs) are presented, wherein aligned CNT films direct the crystallization and orientation of C 60 rods from solution. In these hybrid films, the C 60 rods are oriented parallel to the direction of the CNTs throughout the thickness of the film. High-resolution imaging shows that the crystals incorporate CNTs during growth, yet grazing-incidence X-ray diffraction (GIXD) shows that the crystal structure of the C 60 rods is not perturbed by the CNTs. Growth kinetics of the C 60 rods are enhanced 8-fold on CNTs compared to bare Si, emphasizing the importance of the aligned, porous morphology of the CNT films as well as the selective surface interactions between C 60 and CNTs. Finally, it is shown how hybrid C 60-CNT films can be integrated electrically and employed as UV detectors with a high photoconductive gain and a responsivity of 10 5 A W -1 at low biases (± 0.5 V). The finding that CNTs can induce rapid, directional crystallization of molecules from solution may have broader implications to the science and applications of crystal growth, such as for inorganic nanocrystals, proteins, and synthetic polymers. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bending of nanoscale filament assemblies by elastocapillary densification

We report a mechanism by which nanoscale filaments self-assemble into asymmetric aggregates by elastocapillary action. Specifically, capillary rise of liquid into an asymmetric pattern of vertically aligned filaments causes the filaments to deflect laterally during elastocapillary densification. We quantitatively show that the lateral deflection can be controlled precisely by the pattern shape and the coupling strength among the filaments. We exploit this mechanism to fabricate asymmetric micropillars and multidirectional bridges of densely packed carbon nanotubes. Analogous behavior occurs as biological filaments interact with liquids, and these findings enable scalable fabrication of anisotropic filament assemblies for manipulating surface interactions between solids and liquids. © 2010 The American Physical Society.

Evanescent field sensing: optical nanofibres, whispering-gallery-mode microspherical and microbubble resonators

In this thesis, the evanescent field sensing techniques of tapered optical nanofibres and microspherical resonators are investigated. This includes evanescent field spectroscopy of a silica nanofibre in a rubidium vapour; thermo-optical tuning of Er:Yb co-doped phosphate glass microspheres; optomechanical properties of microspherical pendulums; and the fabrication and characterisation of borosilicate microbubble resonators. Doppler-broadened and sub-Doppler absorption spectroscopic techniques are performed around the D2 transition (780.24 nm) of rubidium using the evanescent field produced at the waist of a tapered nanofibre with input probe powers as low as 55 nW. Doppler-broadened Zeeman shifts and a preliminary dichroic atomic vapour laser lock (DAVLL) line shape are also observed via the nanofibre waist with an applied magnetic field of 60 G. This device has the potential for laser frequency stabilisation while also studying the effects of atom-surface interactions. A non-invasive thermo-optical tuning technique of Er:Yb co-doped microspheres to specific arbitrary wavelengths is demonstrated particularly to 1294 nm and the 5S1/2F=3 to 5P3/2Fʹ=4 laser cooling transition of 85Rb. Reversible tuning ranges of up to 474 GHz and on resonance cavity timescales on the order of 100 s are reported. This procedure has prospective applications for sensing a variety of atomic or molecular species in a cavity quantum electrodynamics (QED) experiments. The mechanical characteristics of a silica microsphere pendulum with a relatively low spring constant of 10-4 Nm-1 are explored. A novel method of frequency sweeping the motion of the pendulum to determine its natural resonance frequencies while overriding its sensitivity to environmental noise is proposed. An estimated force of 0.25 N is required to actuate the pendulum by a displacement of (1-2) μm. It is suggested that this is of sufficient magnitude to be experienced between two evanescently coupled microspheres (photonic molecule) and enable spatial trapping of the micropendulum. Finally, single-input borosilicate microbubble resonators with diameters <100 μm are fabricated using a CO2 laser. Optical whispering gallery mode spectra are observed via evanescent coupling with a tapered fibre. A red-shift of (4-22) GHz of the resonance modes is detected when the hollow cavity was filled with nano-filtered water. A polarisation conversion effect, with an efficiency of 10%, is observed when the diameter of the coupling tapered fibre waist is varied. This effect is also achieved by simply varying the polarisation of the input light in the tapered fibre where the efficiency is optimised to 92%. Thus, the microbubble device acts as a reversible band-pass to band-stop optical filter for cavity-QED, integrated solid-state and semiconductor circuit applications.

Characterisation and spectroscopy of laser-cooled atoms with an optical nanofibre

In this thesis, a magneto-optical trap setup is used to laser cool and confine a cloud of 85Rb. The cloud typically contains 108 atoms in a 1 mm3 volume at a temperature in the region of the Doppler Limit (146 _K for 85Rb). To study the cold cloud, a subwavelength optical fibre - a nanofibre, or ONF - is positioned inside the cloud. The ONF can be used in two ways. Firstly, it is an efficient fluorescence collection tool for the cold atoms. Loading times, lifetimes and temperatures can be measured by coupling the atomic fluorescence to the evanescent region of the ONF. Secondly, the ONF is used as a probe beam delivery tool using the evanescent field properties of the device, allowing one to perform spectroscopy on few numbers of near-surface atoms. With improvements in optical density of the cloud, this system is an ideal candidate in which to generate electromagnetically induced transparency and slow light. A theoretical study of the van der Waals and Casimir-Polder interactions between an atom and a dielectric surface is also presented in this work in order to understand their effects in the spectroscopy of near-surface atoms.

Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems

Coloured effluents from textile industries are a problem in many rivers and waterways. Prediction of adsorption capacities of dyes by adsorbents is important in design considerations. The sorption of three basic dyes, namely Basic Blue 3, Basic Yellow 21 and Basic Red 22, onto peat is reported. Equilibrium sorption isotherms have been measured for the three single component systems. Equilibrium was achieved after twenty-one days. The experimental isotherm data were analysed using Langmuir, Freundlich, Redlich-Peterson, Temkin and Toth isotherm equations. A detailed error analysis has been undertaken to investigate the effect of using different error criteria for the determination of the single component isotherm parameters and hence obtain the best isotherm and isotherm parameters which describe the adsorption process. The linear transform model provided the highest R2 regression coefficient with the Redlich-Peterson model. The Redlich-Peterson model also yielded the best fit to experimental data for all three dyes using the non-linear error functions. An extended Langmuir model has been used to predict the isotherm data for the binary systems using the single component data. The correlation between theoretical and experimental data had only limited success due to competitive and interactive effects between the dyes and the dye-surface interactions.

Magneto-optical trapping and background-free imaging for atoms near nanostructured surfaces

We demonstrate a combined magneto-optical trap and imaging system that is suitable for the investigation of cold atoms near surfaces. In particular, we are able to trap atoms close to optically scattering surfaces and to image them with an excellent signal-to-noise ratio. We also demonstrate a simple magneto-optical atom cloud launching method. We anticipate that this system will be useful for a range of experimental studies of novel atom-surface interactions and atom trap miniaturization.

Mapping piezoelectric nonlinearity in the Rayleigh regime using band excitation piezoresponse force microscopy

Band excitation piezoresponse force microscopy enables local investigation of the nonlinear piezoelectric behavior of ferroelectric thin films. However, the presence of additional nonlinearity associated with the dynamic resonant response of the tip-surface junction can complicate the study of a material's nonlinearity. Here, the relative importance of the two nonlinearity sources was examined as a function of the excitation function. It was found that in order to minimize the effects of nonlinear tip-surface interactions but achieve good signal to noise level, an optimal excitation function must be used. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3593138]

Modification des propriétés optiques de nanofils à base de GaN par plasma N2/O2

Une sonde électrostatique de Langmuir cylindrique a été utilisée pour caractériser une post-décharge d’un plasma d’ondes de surface de N2-O2 par la mesure de la densité des ions et électrons ainsi que la température des électrons dérivée de la fonction de distribution en énergie des électrons (EEDF). Une densité maximale des électrons au centre de la early afterglow de l’ordre de 1013 m-3 a été déterminée, alors que celle-ci a chuté à 1011 m-3 au début de la late afterglow. Tout au long du profil de la post-décharge, une densité des ions supérieure à celle des électrons indique la présence d’un milieu non macroscopiquement neutre. La post-décharge est caractérisée par une EEDF quasi maxwellienne avec une température des électrons de 0.5±0.1 eV, alors qu’elle grimpe à 1.1 ±0.2 eV dans la early afterglow due à la contribution des collisions vibrationnelles-électroniques (V-E) particulièrement importantes. L’ajout d’O2 dans la décharge principale entraîne un rehaussement des espèces chargées et de la température des électrons suivi d’une chute avec l’augmentation de la concentration d’O2. Le changement de la composition électrique de la post-décharge par la création de NO+ au détriment des ions N2+ est à l’origine du phénomène. Le recours à cette post-décharge de N2 pour la modification des propriétés d’émission optique de nanofils purs de GaN et avec des inclusions d’InGaN a été étudié par photoluminescence (PL). Bien que l’émission provenant des nanofils de GaN et de la matrice de GaN recouvrant les inclusions diminue suite à la création de sites de recombinaison non radiatifs, celle provenant des inclusions d’InGaN augmente fortement. Des mesures de PL par excitation indiquent que cet effet n’est pas attribuable à un changement de l’absorption de la surface de GaN. Ceci suggère un recuit dynamique induit par la désexcitation des métastables de N2 suite à leur collision à la surface des nanofils et la possibilité de passiver les défauts de surface tels que des lacunes d’azote par l’action d’atomes de N2 réactifs provenant de la post-décharge. L’incorporation d’O2 induit les mêmes effets en plus d’un décalage vers le rouge de la bande d’émission des inclusions, suggérant l’action des espèces d’O2 au sein même des nanostructures.