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The design of biocompatible synthetic surfaces is an important issue for medical applications. Surface modification techniques provide good approaches to control the interactions between living systems and implanted materials by modifying the surface characteristics. This thesis work demonstrates the feasibility and effectiveness of the novel and low-cost electrostatic self-assembly (ESA) technique for the manufacturing of biocompatible thin film coatings. The ESA process is based on the alternating adsorption of molecular layers of oppositely charged polymers/nanoparticles, and can be applied in the fabrication of well-organized multilayer thin films possessing various biocompatible properties. ESA multilayer assemblies incorporating various biomaterials including metal oxides and polymers were fabricated, the uniformity, thickness, layer-by-layer linearity, and surface morphology of the films were characterized by UV/vis spectroscopy, ellipsometry, and AFM imaging. Preliminary biocompatibility testing was conducted, concentrating on contact angle surface characterization and the in vitro measurements of protein adsorption. The use of Fourier Transform Infrared Reflection-Absorption Spectroscopy (FT-IRAS) for the investigation of the protein adsorption behavior upon the ESA multilayer films is presented. / Master of Science

Nanostructured systems composed of two or more technologically important materials are useful for device applications and intriguing for the new fundamental physics they may display. Magnetism at the nanoscale is dominated by size and surface effects which combined with other media lead to new spin dynamics and interfacial coupling phenomena. These new properties may prove to be useful for optimizing sensors and devices, increasing storage density for magnetic media, as well as for biomedical applications such as drug delivery, MRI contrast enhancement, and hyperthermia treatment for cancer. In this project we have examined the surface and interface magnetism of composite nanoparticles and multilayer thin films by using conventional DC magnetization and AC susceptibility as well as transverse susceptibility, a method for directly probing the magnetic anisotropy of materials. Au and Fe3O4 synthesized together into three different nanoparticle configurations and ranging in size for 60 nm down to 9nm are used to study how the size, shape, and interfaces affect the most fundamental properties of magnetism in the Au-Fe3O4 system. The findings have revealed ways in which the magnetic properties can be enhanced by tuning these parameters. We have shown that by changing the configurations of the Au and Fe3O4 particles, exotic behavior can be observed such as a large increase in anisotropy field (H[subscript]K ranging from 435 Oe to 1650 Oe) and the presence of exchange bias. Multilayer thin films have been studied as well which combine the important classes of ferromagnetic and ferroelectric materials. In one case, barium hexaferrite/barium strontium titanate thin films, the anisotropic behavior of the ferromagnet is shown to change due to the introduction of the secondary material. In the other example, CrO2/Cr2O3 bilayers, exchange coupling is observed as Cr2O3 is an antiferromagnet as well as a ferroelectric. This coupling is manifest as a uniaxial anisotropy rather than the unidirectional anisotropy associated with exchange biased bilayers. Not only will such multifunctional structures will be useful for technological applications, but the materials properties and configurations can be chosen and tuned to further enhance the desired functional properties.

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FePt films with the L10 phase have potential applications for magnetic recording and permanent magnets due to its high magnetocrystalline anisotropy energy density. Heat treatment of n multilayer films is one approach to form the L10 FePt phase through a solid state reaction. This thesis has studied the diffusion and reaction of n multilayer films to form the L10 FePt phase and has used this understanding to construct exchange spring magnets. The process-structure-property relations of n multilayer films were systematically examined. The transmission electron microscopy (TEM) study of the annealed multilayers indicates that the Pt layer grows at the expense of Fe during annealing, forming a disordered fcc FePt phase by the interdiffusion of Fe into Pt. This thickening of the fcc Pt layer can be attributed to the higher solubilities of Fe into fcc Pt, as compared to the converse. For the range of film thickness studied, a continuous L10 FePt product layer that then thickens with further annealing is not found. Instead, the initial L10 FePt grains are distributed mainly on the grain boundaries within the fcc FePt layer and at the Fe/Pt interfaces and further transformation of the sample to the ordered L10 FePt phase proceeds coupled with the growth of the initial L10 FePt grains. A comprehensive study of annealed n films is provided concerning the phase fraction, grain size, nucleation/grain density, interdiffusivity, long-range order parameter, and texture, as well as magnetic properties. A method based on hollow cone dark field TEM is introduced to measure the volume fraction, grain size, and density of ordered L10 FePt phase grains in the annealed films, and low-angle X-ray diffraction is used to measure the effective Fe-Pt interdiffusivity. The process-structure-properties relations of two groups of samples with varying substrate temperature and periodicity are reported. The results demonstrate that the processing parameters (substrate temperature, periodicity) have a strong influence on the structure (effective interdiffusivity, L10 phase volume fraction, grain size, and density) and magnetic properties. The correlation of these parameters suggests that the annealed n multilayer films have limited nuclei, and the subsequent growth of L10 phase is very important to the extent of ordered phase formed. A correlation between the grain size of fcc FePt phase, grain size of the L10 FePt phase, the L10 FePt phase fraction, and magnetic properties strongly suggests that the phase transformation of fccL10 is highly dependent on the grain size of the parent fcc FePt phase. A selective phase growth model is proposed to explain the phenomena observed. An investigation of the influence of total film thickness on the phase formation of the L10 FePt phase in n multilayer films and a comparison of this to that of FePt co-deposited alloy films is also conducted. A general trend of greater L10 phase formation in thicker films was observed in both types of films. It was further found that the thickness dependence of the structure and of the magnetic properties in n multilayer films is much stronger than that in FePt alloy films. This is related to the greater chemical energy contained in n films than FePt alloy films, which is helpful for the L10 FePt phase growth. However, the initial nucleation temperature of n multilayers and co-deposited alloy films was found to be similar. An investigation of L10 FePt-based exchange spring magnets is presented based on our understanding of the L10 formation in n multilayer films. It is known that exchange coupling is an interfacial magnetic interaction and it was experimentally shown that this interaction is limited to within several nanometers of the interface. A higher degree of order of the hard phase is shown to increase the length scale slightly. Two approaches can be used to construct the magnets. For samples with composition close to stoichiometric L10 FePt, the achievement of higher energy product is limited by the average saturation magnetization, and therefore, a lower annealing temperature is beneficial to increase the energy product, allowing a larger fraction of disordered phase. For samples with higher Fe concentration, the (BH)max is limited by the low coercivity of annealed sample, and a higher annealing temperature is beneficial to increase the energy product.

This thesis studies different Eu optical centers in MgS:Eu and CaS:Eu thin films produced by Chemically Controlled Pulse Laser Deposition (CCPLD) and evaluates their suitability for the development of spectral storage devices of the future. The produced thin films consist of one or more optically active layer(s), MgS:Eu, CaS:Eu or a similar material, and a corresponding ZnS capping layer that functions as a protecting barrier for the other layers and preserves their composition and integrity. Given that the synthesis of the materials used to produce the multilayer structures in this work proved a great challenge, careful attention was given to the optimization of all fabrication parameters. Mass Spectrometry was used during the deposition of the thin films and the data obtained resulted on improvements and optimization of the deposition process. Scanning electron microscopy studies of these thin films were conducted to study degradation upon long-term storage. Microscopy results show that the morphology of the produced thin films is correlated to the growth environment during deposition and deterioration of the deposited materials could be initiated by nano-gaps and cracks in the capping layer of the thin films. In addition to optical centers in MgS:Eu and CaS:Eu, new centers were created by changing the thin film growth environment inside a hi-vacuum chamber, modifying the composition of the ablation target material, or both. For example, introducing O2, or alternatively HCl, inside the CCPLD chamber while producing MgS:Eu thin films results in the formation of impurity associated centers across lattice sites throughout the deposited structures. In another method of impurity doping studied, Cl- and Na+ were introduced into the MgS:Eu and CaS:Eu lattices by mixing trace amounts of the impurity ions into these materials in polycrystalline form and making this mixture a deposition target by hi-pressure cold compression technique. The introduction of these impurity ions will alter the crystal field environment around the Eu ions thus creating new optical centers with a shift in energy of their characteristic Zero Phonon Line. After extensive characterization of the optical properties of the thin films produced, laser-induced fluorescence spectroscopy and absorption spectroscopy measurements confirm that they are suitable candidates to be used in conjunction with power-gated spectral holeburning technique and could potentially provide ultrahigh, terabits per square inch, storage densities. / Physics

Layer-by-layer assembly of polyelectrolytes is a simple technique based on the self-assembly of polycations and polyanions mainly by electrostatic interactions, which has gained considerable scientific interest for its versatility of applications. Ease of fabrication process, inexpensive approach and use to coat surfaces with various geometries prompts the researchers to select this technique not only for the surface modification applications but also to study the processes which exploit the 3D matrix properties of polyelectrolyte multilayer films (PEMs). Recent advances have been made where PEMs coatings have been utilized for their bio-applications like drug delivery and in tissue engineering for modifying the biomaterial's surfaces. In the field of drug delivery and tissue engineering the location and availability of the constituent molecules is very important, which is defined by their ability to diffuse through the encapsulating material or reservoir. So the main objective of this thesis is to understand the transport of molecules in ultrathin Polyelectrolyte Multilayer Films in lateral as well as transverse direction to the substrate. To study this transport behaviour in PEMs, we have employed various strategies which can enhance or suppress the diffusivity across PEMs. Thus, understanding the diffusion at nanoscale resolution will lead us to design better host materials for loading of drugs and growth factors for various biomedical applications.

The present thesis focuses on the selection of polymers and methods to fabricate stable and stimuli responsive multilayer self-assembly via layer-by-layer (LbL) approach. The polymers utilized in this study are biodegradable and biocompatible such as hyaluronic acid, chitosan and poly(vinyl alcohol) (PVA). The thesis is comprised of six chapters and a brief discussion on the contents of the individual chapters is given below. Chapter I reviews the LbL self-assembly approach in the context of drug delivery. The various interactions such as electrostatic, hydrogen bonding and covalent bonding involved in preparation of stable multilayer assemblies via LbL approach are discussed. Stimuli responsive behaviour of these multilayer assemblies can be tuned by choosing suitable depositing materials and method. Preparation of hollow microcapsules using LbL approach and its application in drug delivery has also been described in this chapter. Chapter II deals with the LbL assembly of a neutral polymer, poly(vinyl alcholol) (PVA). The negative charge on PVA backbone was induced by physical cross-linking with borax. The PVA-borate can undergo electrostatic interaction with positively charged chitosan in LbL process to form multilayer thin film. The thin film of PVA-borate complex/chitosan was found be responsive towards glucose concentration; disintegration of the multilayer assembly was observed at a high glucose concentration. This finding was rationalized on the basis of strong interaction of glucose with borate ions leading to dissociation of PVA-borate complex and subsequent collapse of the assembly. Thus, this multilayer self-assembly is potent for glucose triggered drug delivery. Chapter III reports the construction of a stable hydrogen bonded multilayer self-assembly based on complementary DNA base pairs (adenine and thymine) interaction. The natural polymer such as chitosan was modified with adenine whereas hyaluronic acid was modified with thymine. These two modified polymers were sequentially deposited on flat substrate and melamine formaldehyde (MF) particles; wherein strong interaction among the DNA base pairs led to the formation of stable assembly without utilizing any external cross-linking agent. The modified polymers are non-cytotoxic as proved from MTT assay. Further the multilayer assembly was used for pH responsive anticancer drug doxorubicin hydrochloride (DOX) release. In Chapter IV, glutaraldehyde mediated LbL self-assembly of single polymer multilayer thin films on flat and colloidal substrate by covalent bonding is described. A comparitive study between the native polymer (chitosan) and adenine modified polymer in the growth of thin film is performed. It is established from the study that the conformation of polymer and the availability of cross-linking points on the polymer play a crucial role in controlling the growth of these multilayer assemblies. Chapter V is divided into two parts (A and B). Part A describes a simple and unique protocol for fabrication of water dispersed chitosan nanoparticles (CH NPs). The method utilized in this work is based on the fast desolvation technique without using any additional stabilizer or any sophisticated instrumental setup. Furthermore, the CH NPs prepared from the mentioned protocol were proved to be cell-viable and are found to be responsive towards pH of the solution. In part B of this chapter, the LbL self-assembly of the responsive CH NPs is fabricated via electrostatic interaction with hyaluronic acid (HA). The growth of the multilayer thin film was found to be linear as function of number of bilayers. The morphology of thin film was characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The microscopic images reveal the uniform film morphology devoid of any phase separation of nanoparticles and polymers. Subsequently, the film was loaded with an anticancer therapeutic, doxorubicin hydrochloride (DOX). The release dynamics of encapsulated drug from the self-assembly are tunable and pH responsive. Chapter VI deals with the general and versatile method for the encapsulation of hydrophobic model drugs into polymeric multilayer assembly by using LbL approach. Electrical charge was induced on the surface of pyrene (uncharged organic substance) using an amphiphilic surfactant, sodium dodecyl sulfate (SDS) by micellar solubilization. The SDS micellar solution of pyrene was utilized to grow LbL multilayer thin film on a planar substrate and colloidal particles along with chitosan as a polycation. The LbL self-assembly of pyrene loaded SDS micelles/chitosan is additionally able to encapsulate hydrophobic or hydrophilic model therapeutics, thus providing an opportunity for dual-drug delivery. The desorption kinetics of the two model drugs from the thin film is found to follow a second order rate model.

Two technologies, namely Laser Technology and Surface Modification Technology, have made rapid strides in the last few decades. The lasers have evolved from a simple laboratory curiosity to a matured industrial tool and its applications are limited only by imagination. Intense, coherent and monochromatic laser sources with power outputs ranging over several orders of magnitude have found innumerable applications in the realm of materials engineering. Reactive Pulsed Laser Deposition (PLD) is a powerful technique that utilises the power of a nanosecond pulsed laser for materials synthesis. Unlike conventional PLD, which require high density targets that are difficult to synthesize at a reasonable cost, the RPLD circumvents the need for one such ceramic target. This thesis presents a detailed and judicious use of this technique for synthesis of hard ceramic multilayer coatings using elemental metal targets. Transition metal nitrides having rock salt structure are known to exhibit superior properties such as hardness and wear resistance and hence formed the basis for the development of first generation coatings. Further improvements through alloying of these binary compounds with metal or metalloid components lead to the development of second generation coatings. As the demand for functional materials increased, surface modification technology alias surface engineering, grew in leaps and bounds. As the large number of coating requirements for optimal performance could not be fulfilled by a single homogeneous material, third generation coatings, comprising multilayer coatings, were developed. It is this aspect of combining the advantages of RPLD process to synthesize ceramic multilayer coatings, provides the main motivation for the present research work. In this thesis, a systematic study presented for synthesis of nanocrystalline and stoichiometric TiN and NbN thin films using RPLD through ablation of high purity titanium and niobium targets, in the presence of low pressure nitrogen gas. A novel Secondary Ion Mass Spectrometry (SIMS) based analysis was developed to effectively deduce the important process parameters in minimum trials to arrive at desired composition. The validity of this SIMS based method, for optimization of process parameters to get stoichiometric nitride films, was proved beyond any speculation by corroborative Proton Elastic Backscattering Spectrometric (PEBS) analysis. SIMS was also used to characterize the [NbN/TiN] multilayers. The feasibility of growing nanocrystalline multilayers with varying thicknesses has been demonstrated. Nanomechanical properties including hardness and adhesion strength of monolithic TiN and NbN films and multilayers were evaluated. The thesis is organised into six chapters. The first chapter gives a brief account on the history and development of ‘surface engineering’. The second chapter provides a comprehensive description of the experimental facility developed in-house to pursue research on PLD grown ceramic thin films and multilayers. Thin film synthesis procedure for ex-situ SIMS and TEM analyses is described. Brief introduction is also presented on the characterization techniques used in this study to investigate the surface, interface and microstructural aspects of PLD grown films with underlying basic principles. The third and fourth chapter describes the synthesis and characterization of titanium nitride and niobium nitride thin films using RPLD technique, respectively. SIMS was used in depth profiling mode, for optimization of three important process parameters, viz., nitrogen gas pressure, substrate temperature and laser pulse energy, to get stoichiometric nitride films. Further, films were characterized using GIXRD, TEM, XPS and PEBS for their structure and composition. AFM measurements were made to elucidate the surface morphological features. PEBS was effectively used to estimate the nitrogen concentration in a quantitative manner and the results corroborate well with the SIMS measurements. Having succeeded in synthesizing stoichiometric TiN and NbN films, further studies on the nanomechanical properties of monolithic TiN and NbN films and their multilayers were carried out and these results form the contents of the fifth chapter. The findings of the work reported in this thesis are concluded in Chapter 6 and few possible suggestions were presented as future directions. Both the monolithic TiN and NbN coatings showed a deposition pressure dependent hardness variation. The hardness of these monolithic films was found to be around 30 GPa, higher than the hardness values obtained by other conventional techniques. Keeping total thickness of the multilayers constant at 1 μm, [NbN/TiN] multilayers having bilayer periods ranging from 50 nm to 1000 nm, were synthesized. A systematic enhancement in hardness upto ~ 40 GPa was observed for [NbN/TiN]10 with the modulus of the multilayer remaining almost constant. The pileup observed around the indentation edge is indicative of toughening in multilayers. The tribological properties of multilayer films showed a better performance in terms of low coefficient of friction and regeneration of coating surfaces as revealed from the nanotribological studies. Overall, the multilayer coatings exhibited better performance in terms of hardness, toughness and adhesion with the substrate material.