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Thin films are nanoscale layers of material, with exotic properties useful in diverse areas, ranging from biomedicine to nanoelectronics and surface protection. Film properties are not only determined by their chemical composition, but also by their microstructure and roughness, features that depend crucially on the growth process due to the inherent out-of equilibrium nature of the film deposition techniques. This fact suggest that it is possible to control film growth, and in turn film properties, in a knowledge-based manner by tuning the deposition conditions. This requires a good understanding of the elementary film-forming processes, and the way by which they are affected by atomic-scale kinetics. The kinetic Monte Carlo (kMC) method is a simulation tool that can model film evolution over extended time scales, of the order of microseconds, and beyond, and thus constitutes a powerful complement to experimental research aiming to obtain an universal understanding of thin film formation and morphological evolution. In this work, kMC simulations, coupled with analytical modelling, are used to investigate the early stages of formation of metal films and nanostructures supported on weakly-interacting substrates. This starts with the formation and growth of faceted 3D islands, that relies first on facile adatom ascent at single-layer island steps and subsequently on facile adatom upward diffusion from the base to the top of the island across its facets. Interlayer mass transport is limited by the rate at which adatoms cross from the sidewall facets to the island top, a process that determines the final height of the islands and leads non-trivial growth dynamics, as increasing temperatures favour 3D growth as a result of the upward transport. These findings explain the high roughness observed experimentally in metallic films grown on weakly-interacting substrates at high temperatures. The second part of the study focus on the next logical step of film formation, when 3D islands come into contact and fuse into a single one, or coalesce. The research reveals that the faceted island structure governs the macroscopic process of coalescence as well as its dynamics, and that morphological changes depend on 2D nucleation on the II facets. In addition, deposition during coalescence is found to accelerate the process and modify its dynamics, by contributing to the nucleation of new facets. This study provides useful knowledge concerning metal growth on weakly-interacting substrates, and, in particular, identifies the key atomistic processes controlling the early stages of formation of thin films, which can be used to tailor deposition conditions in order to achieve films with unique properties and applications.
Vapor-based growth of thin metal films with controlled morphology on weakly-interacting substrates (WIS), including oxides and van der Waals materials, is essential for the fabrication of multifunctional metal contacts in a wide array of optoelectronic devices. Achieving this entails a great challenge, since weak film/substrate interactions yield a pronounced and uncontrolled 3D morphology. Moreover, the far-from-equilibrium nature of vapor-based film growth often leads to generation of mechanical stress, which may further compromise device reliability and functionality. The objectives of this thesis are related to metal film growth on WIS and seek to: (i) contribute to the understanding of atomic-scale processes that control film morphological evolution; (ii) elucidate the dynamic competition between nanoscale processes that govern film stress generation and evolution; and (iii) develop methodologies for manipulating and controlling nanoscale film morphology between 2D and 3D. Investigations focus on magnetron sputter-deposited Ag and Cu films on SiO2 and amorphous carbon (a-C) substrates. Research is conducted by strategically combining of in situ and real-time film growth monitoring, ex situ chemical and (micro)-structural analysis, optical modelling, and deterministic growth simulations. In the first part, the scaling behavior of characteristic morphological transition thicknesses (i.e., percolation and continuous film formation thickness) during growth of Ag and Cu films on a-C are established as function of deposition rate and temperature. These data are interpreted using a theoretical framework based on the droplet growth theory and the kinetic freezing model for island coalescence, from which the diffusion rates of film forming species during Ag and Cu growth are estimated. By combining experimental data with ab initio molecular dynamics simulations, diffusion of multiatomic clusters, rather than monomers, is identified as the rate-limiting structure-forming process. In the second part, the effect of minority metallic or gaseous species (Cu, N2, O2) on Ag film morphological evolution on SiO2 is studied. By employing in situ spectroscopic ellipsometry, it is found that addition of minority species at the film growth front promotes 2D morphology, but also yields an increased continuous-layer resistivity. Ex situ analyses show that 2D morphology is favored because minority species hinder the rate of coalescence completion. Hence, a novel growth manipulation strategy is compiled in which minority species are deployed with high temporal precision to selectively target specific film growth stages and achieve 2D morphology, while retaining opto-electronic properties of pure Ag films. In the third part, the evolution of stress during Ag and Cu film growth on a-C and its dependence on growth kinetics (as determined by deposition rate, substrate temperature) is systematically investigated. A general trend toward smaller compressive stress magnitudes with increasing temperature/deposition rate is found, related to increasing grain size/decreasing adatom diffusion length. Exception to this trend is found for Cu films, in which oxygen incorporation from the residual growth atmosphere at low deposition rates inhibits adatom diffusivity and decreases the magnitude of compressive stress. The effect of N2 on stress type and magnitude in Ag films is also studied. While Ag grown in N2-free atmosphere exhibits a typical compressive-tensile-compressive stress evolution as function of thickness, addition of a few percent of N2 yields to a stress turnaround from compressive to tensile stress after film continuity which is attributed to giant grain growth and film roughening. The overall results of the thesis provide the foundation to: (i) determine diffusion rates over a wide range of WIS film/substrates systems; (ii) design non-invasive strategies for multifunctional contacts in optoelectronic devices; (iii) complete important missing pieces in the fundamental understanding of stress, which can be used to expand theoretical descriptions for predicting and tuning stress magnitude. La morphologie de films minces métalliques polycristallins élaborés par condensation d’une phase vapeur sur des substrats à faible interaction (SFI) possède un caractère 3D intrinsèque. De plus, la nature hors équilibre de la croissance du film depuis une phase vapeur conduit souvent à la génération de contraintes mécaniques, ce qui peut compromettre davantage la fiabilité et la fonctionnalité des dispositifs optoélectroniques. Les objectifs de cette thèse sont liés à la croissance de films métalliques sur SFI et visent à: (i) contribuer à une meilleure compréhension des processus à l'échelle atomique qui contrôlent l'évolution morphologique des films; (ii) élucider les processus dynamiques qui régissent la génération et l'évolution des contraintes en cours de croissance; et (iii) développer des méthodologies pour manipuler et contrôler la morphologie des films à l'échelle nanométrique. L’originalité de l’approche mise en œuvre consiste à suivre la croissance des films in situ et en temps réel par couplage de plusieurs diagnostics, complété par des analyses microstructurales ex situ. Les grandeurs mesurées sont confrontées à des modèles optiques et des simulations atomistiques. La première partie est consacrée à une étude de comportement d’échelonnement des épaisseurs de transition morphologiques caractéristiques, à savoir la percolation et la continuité du film, lors de la croissance de films polycristallins d'Ag et de Cu sur carbone amorphe (a-C). Ces grandeurs sont examinées de façon systématique en fonction de la vitesse de dépôt et de la température du substrat, et interprétées dans le cadre de la théorie de la croissance de gouttelettes suivant un modèle cinétique décrivant la coalescence d’îlots, à partir duquel les coefficients de diffusion des espèces métalliques sont estimés. En confrontant les données expérimentales à des simulations par dynamique moléculaire ab initio, la diffusion de clusters multiatomiques est identifiée comme l’étape limitante le processus de croissance. Dans la seconde partie, l’incorporation, et l’impact sur la morphologie, d’espèces métalliques ou gazeuses minoritaires (Cu, N2, O2) lors de la croissance de film Ag sur SiO2 est étudié. A partir de mesures ellipsométriques in situ, on constate que l'addition d'espèces minoritaires favorise une morphologie 2D, entravant le taux d'achèvement de la coalescence, mais donne également une résistivité accrue de la couche continue. Par conséquent, une stratégie de manipulation de la croissance est proposée dans laquelle des espèces minoritaires sont déployées avec une grande précision temporelle pour cibler sélectivement des stades de croissance de film spécifiques et obtenir une morphologie 2D, tout en conservant les propriétés optoélectroniques des films d’Ag pur. Dans la troisième partie, l'évolution des contraintes résiduelles lors de la croissance des films d'Ag et de Cu sur a-C et leur dépendance à la cinétique de croissance est systématiquement étudiée. On observe une tendance générale vers des amplitudes de contrainte de compression plus faibles avec une augmentation de la température/vitesse de dépôt, liée à l'augmentation de la taille des grains/à la diminution de la longueur de diffusion des adatomes. Également, l’ajout dans le plasma de N2 sur le type et l'amplitude des contraintes dans les films d'Ag est étudié. L'ajout de quelques pourcents de N2 en phase gaz donne lieu à un renversement de la contrainte de compression et une évolution en tension au-delà de la continuité du film. Cet effet est attribué à une croissance anormale des grains géants et le développement de rugosité de surface. L’ensemble des résultats obtenus dans cette thèse fournissent les bases pour: (i) déterminer les coefficients de diffusion sur une large gamme de systèmes films/SFI; (ii) concevoir des stratégies non invasives pour les contacts multifonctionnels dans les dispositifs optoélectroniques; (iii) apporter des éléments de compréhension à l’origine du développement de contrainte, qui permettent de prédire et contrôler le niveau de contrainte intrinsèque à la croissance de films minces polycristallins.
Thin films are structures consisting of one or several nanoscale atomic layers of material that are used to either functionalize a surface or constitute components in more complex devices. Many properties of a film are closely related to its microstructure, which allows films to be tailored to meet specific technological requirements. Atom-by-atom film growth from the vapor phase involves a multitude of atomic processes that may not be easily studied experimentally in real-time because they occur in small length- (? Å) and timescales (? ns). Therefore, different types of computer simulation methods have been developed in order to test theoretical models of thin film growth and unravel what experiments cannot show. In order to compare simulated and experimental results, the simulations must be able to model events on experimental time-scales, i.e. on the order of microseconds to seconds. This is achievable with the kinetic Monte Carlo (kMC) method. In this work, the initial growth stages of metal deposition on weakly-interacting substrates is studied using both kMC simulations as well as experiments whereby growth was monitored using in situ probes. Such film/substrate material combinations are widely encountered in technological applications including low-emissivity window coatings to parts of microelectronics components. In the first part of this work, a kMC algorithm was developed to model the growth processes of island nucleation, growth and coalescence when these are functions of deposition parameters such as the vapor deposition rate and substrate temperature. The dynamic interplay between these growth processes was studied in terms of the scaling behavior of the film thickness at the elongation transition, for both continuous and pulsed deposition fluxes, and revealed in both cases two distinct growth regimes in which coalescence is either active or frozen out during deposition. These growth regimes were subsequently confirmed in growth experiments of Ag on SiO2, again for both pulsed and continuous deposition, by measuring the percolation thickness as well as the continuous film formation thickness. However, quantitative agreement with regards to scaling exponents in the two growth regimes was not found between simulations and experiments, and this prompted the development of a method to determine the elongation transition thickness experimentally. Using this method, the elongation transition of Ag on SiO2 was measured, with scaling exponents found in much better agreement with the simulation results. Further, these measurement data also allowed the calculation of surface properties such as the terrace diffusion barrier of Ag on SiO2 and the average island coalescence rate. In the second part of this thesis, pioneering work is done to develop a fully atomistic, on-lattice model which describes the growth of Ag on weakly-interacting substrates. Simulations performed using this model revealed several key atomic-scale processes occurring at the film/substrate interface and on islands which govern island shape evolution, thereby contributing to a better understanding of how 3D island growth occurs at the atomic scale for a wide class of materials. The latter provides insights into the directed growth of metal nanostructures with controlled shapes on weakly-interacting substrates, including twodimensional crystals for use in catalytic and nano-electronic applications.
This Special Issue deals with the synthesis of nanostructured surfaces and thin films by means of physical vapor deposition techniques such as pulsed laser deposition, magnetron sputtering, HiPIMS, or e-beam evaporation, among others. The nanostructuration of the surface modifies the way a material interacts with the environment, changing its optical, mechanical, electrical, tribological, or chemical properties. This can be applied in the development of photovoltaic cells, tribological coatings, optofluidic sensors, or biotechnology to name a few. This issue includes research presenting novel or improved applications of nanostructured thin films, such as photovoltaic solar cells, thin-film transistors, antibacterial coatings or chemical and biological sensors, while also studying the nanostructuration mechanisms, from a fundamental point of view, that produce rods, columns, helixes or hexagonal grids at the nanoscale.
High Power Impulse Magnetron Sputtering: Fundamentals, Technologies, Challenges and Applications is an in-depth introduction to HiPIMS that emphasizes how this novel sputtering technique differs from conventional magnetron processes in terms of both discharge physics and the resulting thin film characteristics. Ionization of sputtered atoms is discussed in detail for various target materials. In addition, the role of self-sputtering, secondary electron emission and the importance of controlling the process gas dynamics, both inert and reactive gases, are examined in detail with an aim to generate stable HiPIMS processes. Lastly, the book also looks at how to characterize the HiPIMS discharge, including essential diagnostic equipment. Experimental results and simulations based on industrially relevant material systems are used to illustrate mechanisms controlling nucleation kinetics, column formation and microstructure evolution.
This 3e, edited by Peter M. Martin, PNNL 2005 Inventor of the Year, is an extensive update of the many improvements in deposition technologies, mechanisms, and applications. This long-awaited revision includes updated and new chapters on atomic layer deposition, cathodic arc deposition, sculpted thin films, polymer thin films and emerging technologies. Extensive material was added throughout the book, especially in the areas concerned with plasma-assisted vapor deposition processes and metallurgical coating applications.
Handbook of Modern Coating Technologies: Advanced Characterization Methods reviews advanced characterization methods of modern coating technologies. The topics in this volume consist of scanning vibrating electrode technique, spectroscopic ellipsometry, advances in X-ray diffraction, neutron reflectivity, micro- and nanoprobes, fluorescence technique, stress measurement methods in thin films, micropotentiometry, and localized corrosion studies.
This textbook is for graduate students and young scientists, who are looking for an introduction to the physics and physical chemistry of crystal growth and nucleation phenomena.
This practical book shows how an understanding of structure, thermodynamics, and electrical properties can explain some of the choices of materials used in microelectronics, and can assist in the design of new materials for specific applications. It emphasizes the importance of the phase chemistry of semiconductor and metal systems for ensuring the long-term stability of new devices. The book discusses single-crystal and polycrystalline silicon, aluminium- and gold-based metallisation schemes, packaging semiconductor devices, failure analysis, and the suitability of various materials for optoelectronic devices and solar cells. It has been designed for senior undergraduates, graduates, and researchers in physics, electronic engineering, and materials science.