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The morphology of numerous nanocolumnar thin films deposited by the magnetron sputtering technique at oblique geometries and at relatively low temperatures has been analyzed for materials as different as Au, Pt, Ti, Cr, TiO₂, Al, HfN, Mo, V, WO₃ and W. Despite similar deposition conditions, two characteristic nanostructures have been identified depending on the material: a first one defined by highly tilted and symmetric nanocolumnar structures with a relatively high film density, and a second one characterized by rather vertical and asymmetric nanocolumns, with a much lower film density. With the help of a model, the two characteristic nanostructures have been linked to different growth dynamics and, specifically, to different surface relaxation mechanisms upon the incorporation of gaseous species with kinetic energies above the surface binding energy. Moreover, in the case of Ti, a smooth structural transition between the two types of growths has been found when varying the value of the power used to maintain the plasma discharge. Based on these results, the existence of different surface relaxation mechanisms is proposed, which quantitatively explains numerous experimental results under the same conceptual framework.

En esta Tesis Doctoral Industrial se estudia la problemática del diseño de un sistema de deposición de pulverización catódica en geometría de ángulo oblicuo en escalas y condiciones industriales para operar sobre superficies rugosas de grado industrial. Esta técnica, de amplio uso, se suele utilizar para hacer recubrimientos de tipo compacto en su geometría clásica, mientras que su uso a ángulo oblicuo, responsable del crecimiento nanocolumnar, está restringido a laboratorios de investigación debido a las numerosas restricciones que impone dicha geometría de trabajo, e. g. inhomogeneidad de los recubrimientos, dificultad para producción en serie, imposibilidad de operar sobre grandes superficies, etc. En pequeñas superficies, los recubrimientos nanocolumnares son bien conocidos por poseer propiedades singulares asociadas a su baja densidad y a la alta superficie específica de las nanocolumnas. Es por esto que el desarrollo de esta técnica en escalas operativas industriales resulta clave para su incorporación en diferentes dispositivos tecnológicos y para el desarrollo de aplicaciones basadas en ellas..., This industrial PhD Thesis aims at studying the problems associated with the design of a magnetron sputtering reactor to operate at oblique angle geometries over large industrial rough substrates. This technique, in its classical non-oblique configuration, is widely employed in research laboratories and in the industry to coat large surfaces with compact homogeneous thin films. Yet, the use of the oblique angle configuration is currently constrained to conditions found in research laboratories, such as the requirement of small-scale and ultrasmooth flat substrates. Also, some consequences of the use of this configuration, e.g. thin film inhomogeneity, or the impossibility to operate on roll-to-roll systems, for instance, have prevented until now its implementation at industrial scales. On small laboratory-size substrates, the films produced at oblique geometries are formed by a disordered array of tilted nanocolumns, with diameter ~100 nm and separated side-to-side a similar distance. This gives these films high porosity, low density, and high specific surface, which confer them unique and remarkable properties, with applications in fields as different as sensors, optics, microelectronics, optoelectronics, plasmonics, microfluidics, etc. Consequently, the development of a clear strategy to grow this type of films at industrial scales represents a fundamental key challenge to develop/improve numerous state of the art technological devices...

The morphology and void connectivity of thin films grown by a magnetron sputtering deposition technique at oblique geometries were studied in this paper. A well-tested thin film growth model was employed to assess the features of these layers along with experimental data taken from the literature. A strong variation in the film morphology and pore topology was found as a function of the growth conditions, which have been linked to the different collisional transport of sputtered species in the plasma gas. Four different characteristic film morphologies were identified, such as (i) highly dense and compact, (ii) compact with large, tilted mesopores, (iii) nanocolumns separated by large mesopores, and (iv) vertically aligned sponge-like coalescent nanostructures. Attending to the topology and connectivity of the voids in the film, the nanocolumnar morphology was shown to present a high pore volume and area connected with the outside by means of mesopores, with a diameter above 2 nm, while the sponge-like nanostructure presented a high pore volume and area, as well as a dense network connectivity by means of micropores, with a diameter below 2 nm. The obtained results describe the different features of the porous network in these films and explain the different performances as gas or liquid sensors in electrochromic applications or for infiltration with nanoparticles or large molecules.

En esta Tesis Doctoral Industrial se estudia la problemática del diseño de un sistema de deposición de pulverización catódica en geometría de ángulo oblicuo en escalas y condiciones industriales para operar sobre superficies rugosas de grado industrial. Esta técnica, de amplio uso, se suele utilizar para hacer recubrimientos de tipo compacto en su geometría clásica, mientras que su uso a ángulo oblicuo, responsable del crecimiento nanocolumnar, está restringido a laboratorios de investigación debido a las numerosas restricciones que impone dicha geometría de trabajo, e. g. inhomogeneidad de los recubrimientos, dificultad para producción en serie, imposibilidad de operar sobre grandes superficies, etc. En pequeñas superficies, los recubrimientos nanocolumnares son bien conocidos por poseer propiedades singulares asociadas a su baja densidad y a la alta superficie específica de las nanocolumnas. Es por esto que el desarrollo de esta técnica en escalas operativas industriales resulta clave para su incorporación en diferentes dispositivos tecnológicos y para el desarrollo de aplicaciones basadas en ellas..., This industrial PhD Thesis aims at studying the problems associated with the design of a magnetron sputtering reactor to operate at oblique angle geometries over large industrial rough substrates. This technique, in its classical non-oblique configuration, is widely employed in research laboratories and in the industry to coat large surfaces with compact homogeneous thin films. Yet, the use of the oblique angle configuration is currently constrained to conditions found in research laboratories, such as the requirement of small-scale and ultrasmooth flat substrates. Also, some consequences of the use of this configuration, e.g. thin film inhomogeneity, or the impossibility to operate on roll-to-roll systems, for instance, have prevented until now its implementation at industrial scales. On small laboratory-size substrates, the films produced at oblique geometries are formed by a disordered array of tilted nanocolumns, with diameter ~100 nm and separated side-to-side a similar distance. This gives these films high porosity, low density, and high specific surface, which confer them unique and remarkable properties, with applications in fields as different as sensors, optics, microelectronics, optoelectronics, plasmonics, microfluidics, etc. Consequently, the development of a clear strategy to grow this type of films at industrial scales represents a fundamental key challenge to develop/improve numerous state of the art technological devices...

In this work, piezoelectric AWs and plasmas have been brought together during the growth of a thin film as a novel methodology of plasma-assisted thin film structuration. The ensuing effects have been investigated on a model system where SiO2 and SiOx (x<2) thin films have been deposited by magnetron sputtering at oblique angles (MS-OAD) on an electro-acoustically excited LiNbO3 piezoelectric substrate under resonant conditions. The microstructure of the resulting films was 2D patterned and depicted submillimeter size intermingled zones with different optical characteristics, compositions (SiO2 and SiOx) and porosity, from highly porous to dense and compact regions. The 2D nanostructural pattern mimics the AW distribution and has been accounted for by means of a specific simulation model. It is concluded that the morphological and chemical film pattern replicates the distribution of polarization potential on the surface of the AW activated substrate immersed in the plasma. Moreover, we show that the main mechanism responsible for the appearance of domains with different morphology and chemical composition is the focused impingement of Ar+plasma ions on certain regions of the substrate. The general character of this patterning process, the underlying physics and its possibilities to tailor the composition and microstructure of dielectric thin film materials are discussed.

It is demonstrated that, besides classical nanocolumnar arrays, the oblique angle geometry induces the growth of singular structures in the nanoscale when using wisely designed patterned substrates. Well-ordered array of crosses, cylindrical nanorods or hole structures arranged in square or hexagonal regular geometries are reported as examples, among others. The fundamental framework connecting substrate topography and film growth at oblique angles is presented, allowing the use of substrate patterning as a feasible thin film nanostructuring technique. A systematic analysis of the growth of TiO2 thin films on 4 different lithographic patterned substrates in 4 different scale lengths is also presented. A first conclusion is the existence of a height-based selective growth in the initial stages of the deposition, by which the film preferentially develops on top of the tallest substrate features. This behavior is maintained until the film reaches a critical thickness, the so-called Oblivion Thickness, above which the film topography becomes gradually independent of the substrate features. A general formula relating the spatial features of the pattern, the coarsening exponent and the Oblivion Thickness has been deduced.

Nanostructuration and 2D patterning of thin films are common strategies to fabricate biomimetic surfaces and components for microfluidic, microelectronic or photonic applications. This work presents the fundamentals of a surface nanotechnology procedure for laterally tailoring the nanostructure and crystalline structure of thin films that are plasma deposited onto acoustically excited piezoelectric substrates. Using magnetron sputtering as plasma technique and TiO2 as case example, it is demonstrated that the deposited films depict a sub-millimetre 2D pattern that, characterized by large lateral differences in nanostructure, density (up to 50%), thickness, and physical properties between porous and dense zones, reproduces the wave features distribution of the generated acoustic waves (AW). Simulation modelling of the AW propagation and deposition experiments carried out without plasma and under alternative experimental conditions reveal that patterning is not driven by the collision of ad-species with mechanically excited lattice atoms of the substrate, but emerges from their interaction with plasma sheath ions locally accelerated by the AW-induced electrical polarization field developed at the substrate surface and growing film. The possibilities of the AW activation as a general approach for the tailored control of nanostructure, pattern size, and properties of thin films are demonstrated through the systematic variation of deposition conditions and the adjustment of AW operating parameters.

En este trabajo se describe la aplicación de un ciclo de mejora en el aula en la asignatura Física II de primer curso del Grado en Ingeniería del Diseño Industrial y Desarrollo del Producto. El modelo metodológico propuesto es de tipo investigativo, donde se plantea una pregunta inicial a los alumnos y éstos proponen hipótesis que deberán testear. Las actividades diseñadas incluyen discusión en grupos, fichas de actividades o visionado de experimentos. La comparación de cuestionarios realizados antes y después del ciclo refleja una mejora importante en los niveles de conocimiento de los alumnos respecto a los contenidos del tema. En una encuesta final, los alumnos declararon unánimemente preferir esta metodología a la tradicional.

The nano-porosity embedded into the tilted and separated nanocolumns characteristic of the microstructure of evaporated thin films at oblique angles has been critically assessed by various variants of the positron annihilation spectroscopy. This technique represents a powerful tool for the analysis of porosity, defects and internal interfaces of materials, and has been applied to different as-deposited SiO2 and TiO2 thin films as well as SiO2/TiO2 multilayers prepared by electron beam evaporation at 70° and 85° zenithal angles. It is shown that, under same deposition conditions, the concentration of internal nano-pores in SiO2 is higher than in TiO2 nanocolumns, while the situation is closer to this latter in TiO2/SiO2 multilayers. These features have been compared with the predictions of a Monte Carlo simulation of the film growth and explained by considering the influence of the chemical composition on the growth mechanism and, ultimately, on the structure of the films.

Unlike topography patterning, widely used for numerous applications and produced by means of different technologies, there are no simple procedures to achieve surface compositional patterning at nanometric scales. In this work we have developed a simple method for 2D patterning the composition of thin films. The method relies on the magnetron sputtering deposition at oblique angles onto patterned substrates made by laser induced periodic surface structures (LIPSS). The method feasibility has been demonstrated by depositing SiOx thin films onto LIPSS structures generated in Cr layers. A heterogeneous and aligned distribution of O/Si ratios (and different Si n+ chemical states) along the LIPSS structure in length scales of some hundreds nm's has been proven by angle resolved X-ray photoelectron spectroscopy and a patterned arrangement of composition monitored by atomic force microscopy-Raman analysis. The obtained results are explained by the predictions of a Monte Carlo simulation of this deposition process and open the way for the tailored one-step fabrication of surface devices with patterned compositions.

Based on an already tested laboratory procedure, a new magnetron sputtering methodology to simultaneously coat two-sides of large area implants (up to ~15 cm2) with Ti nanocolumns in industrial reactors has been developed. By analyzing the required growth conditions in a laboratory setup, a new geometry and methodology have been proposed and tested in a semi-industrial scale reactor. A bone plate (DePuy Synthes) and a pseudo-rectangular bone plate extracted from a patient were coated following the new methodology, obtaining that their osteoblast proliferation efficiency and antibacterial functionality were equivalent to the coatings grown in the laboratory reactor on small areas. In particular, two kinds of experiments were performed: Analysis of bacterial adhesion and biofilm formation, and osteoblasts–bacteria competitive in vitro growth scenarios. In all these cases, the coatings show an opposite behavior toward osteoblast and bacterial proliferation, demonstrating that the proposed methodology represents a valid approach for industrial production and practical application of nanostructured titanium coatings.

We experimentally analyze different growth regimes of Ti thin films associated to the existence of kinetic energy-induced relaxation mechanisms in the material's network when operating at oblique geometries. For this purpose, we have deposited different films by evaporation and magnetron sputtering under similar geometrical arrangements and at low temperatures. With the help of a well-established growth model we have found three different growth regimes: (i) low energy deposition, exemplified by the evaporation technique, carried out by species with typical energies in the thermal range, where the morphology and density of the film can be explained by solely considering surface shadowing processes, (ii) magnetron sputtering under weak plasma conditions, where the film growth is mediated by surface shadowing mechanisms and kinetic-energy-induced relaxation processes, and (iii) magnetron sputtering under intense plasma conditions, where the film growth is highly influenced by the plasma, and whose morphology is defined by nanocolumns with similar tilt than evaporated films, but with much higher density. The existence of these three regimes explains the variety of morphologies of nanocolumnar Ti thin films grown at oblique angles under similar conditions in the literature.

The influence of one dimensional substrate patterns on the nanocolumnar growth of thin films deposited by magnetron sputtering at oblique angles is theoretically and experimentally studied. A well‐established growth model has been used to study the interplay between the substrate topography and the thin film morphology. A critical thickness has been defined, below which the columnar growth is modulated by the substrate topography, while for thicknesses above, the impact of substrate features is progressively lost in two stages; first columns grown on taller features take over neighboring ones, and later the film morphology evolves independently of substrate features. These results have been experimentally tested by analyzing the nanocolumnar growth of SiO2 thin films on ion‐induced patterned substrates.

Traditionally porous silicon based photonic structures have been prepared by electrochemically etching of silicon. In this work, porous multilayers of nanocolumnar SiOx and SiO2 thin films acting as near infrared (NIR) 1D-photonic nanostructures are prepared by magnetron sputtering deposition at oblique angles (MS-OA). Simultaneous control of porosity and stoichiometry of the stacked films is achieved by adjusting the deposition angle and oxygen partial pressure according to a parametric formula. This new methodologoy is proved for the synthesis of SiOx thin films with x close to 0.4, 0.8, 1.2, 1.6 and nanostructures varying from compact (at 0° deposition angle) to highly porous and nanocolumnar (at 70° and 85° deposition angles). The strict control of composition, structure and nanostructure provided by this technique permits a fine tuning of the absorption edge and refraction index at 1500 nm of the porous films and their manufacturing in the form of SiOx-SiO2 porous multilayers acting as near infrared (NIR) 1D-photonic structures with well-defined optofluidic responses. Liquid tunable NIR Bragg mirrors and Bragg microcavities for liquid sensing applications are presented as proof of concept of the possibilities of this MS-OA manufacturing method as an alternative to the conventional electrochemical fabrication of silicon based photonic structures.

The selective incorporation of deposition species with preferential directionality is analyzed during the growth of TiO2 thin films by magnetron sputtering. Using wisely-designed collimators, tilted nanocolumnar morphol- ogies are grown in a ballistic deposition regime, i.e. when most deposition species arrive at the film surface along well-defined preferential directions, and also in a thermalized deposition regime, when these species follow an isotropic momentum distribution in the plasma gas. The obtained results suggest that the use of particle colli- mators may promote the growth of porous thin films even in the classical magnetron sputtering configuration, when the target and the substrate are parallel. General insights are given on this approach and, as a proof of concept, its principles applied for the synthesis of nanostructured films in a laboratory-size reactor.

This paper reports a novel cholesterol biosensor based on nanostructured platinum (Pt) thin films prepared by Magnetron Sputtering (MS) in an oblique angle (OAD) configuration. Pt thin films were deposited onto a gold screen-printed electrode and characterized using Rutherford Back Scattering (RBS), Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Cyclic Voltammetry (CV), X-ray Photo-electron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and wetting analysis. Our results confirmed that the film is highly porous and formed by tilted nanocolumns, with an inclination of around 40° and a total thickness of 280 nm. XRD and CV analysis confirmed the polycrystalline nature of the Pt thin film. Cholesterol oxidase (ChOx) was covalently immobilized using a bioinspired polymer, polydopamine (PDA), via Schiff base formation and Michael-type addition. After being immobilized, ChOx displayed apparent activation energy of 34.09 kJ mol−1 and Michaelis constant (KM) values of 34.09 kJ mol−1 and 3.65 mM, respectively, confirming the high affinity between ChOx and cholesterol and the excellent ability of the PDA film for immobilizing biological material without degradation. Under optimized working conditions the developed biosensor presented a sensitivity of 14.3 mA M−1cm−2 (R2:0.999) with a linear range up to 0.5 mM and a limit of detection of 10.5 μM (S/N = 3). Furthermore, the biosensor exhibited a fast response (<8 s), good anti-interference properties and high stability after relatively long-term storage (2 months).

The fabrication of black-gold coatings using sputtering is reported here. Glancing angle deposition with a rotating substrate is needed to obtain vertical nanostructures. Enhanced light absorption is obtained in the samples prepared in the ballistic regime with high tilt angles. Under these conditions the diameter distribution of the nanostructures is centered at about 60 nm and the standard deviation is large enough to obtain black-metal behavior in the visible range

In this work we analyze a phenomenon that takes place when growing magnetron sputtered porous/compact multilayer systems by alternating the oblique angle and the classical configuration geometries. We show that the compact layers develop numerous fissures rooted in the porous structures of the film below, in a phenomenon that amplifies when increasing the number of stacked layers. We demonstrate that these fissures emerge during growth due to the high roughness of the porous layers and the coarsening of a discontinuous interfacial region. To minimize this phenomenon, we have grown thin interlayers between porous and compact films under the impingement of energetic plasma ions, responsible for smoothing out the interfaces and inhibiting the formation of structural fissures. This method has been tested in practical situations for compact TiO2/porous SiO2 multilayer systems, although it can be extrapolated to other materials and conditions.

The growth of Ti thin films by the magnetron sputtering technique at oblique angles and at room temperature is analysed from both experimental and theoretical points of view. Unlike other materials deposited in similar conditions, the nanostructure development of the Ti layers exhibits an anomalous behaviour when varying both the angle of incidence of the deposition flux and the deposition pressure. At low pressures, a sharp transition from compact to isolated, vertically aligned, nanocolumns is obtained when the angle of incidence surpasses a critical threshold. Remarkably, this transition also occurs when solely increasing the deposition pressure under certain conditions. By the characterization of the Ti layers, the realization of fundamental experiments and the use of a simple growth model, we demonstrate that surface mobilization processes associated to a highly directed momentum distribution and the relatively high kinetic energy of sputtered atoms are responsible for this behaviour

The framework to describe the out-of-equilibrium free electrons in cold plasmas is developed assuming the electron entropy is defined through the Boltzmann H-theorem. Our theory explains why the Saha-Boltzmann relation among higher-lying excited states by means of the electron kinetic temperature is fulfilled, even when free electrons are far from equilibrium. The thermodynamic electron temperature, pressure and chemical potential have been introduced through the derivatives of the electron entropy. It is demonstrated that under usual conditions in cold plasmas, e.g. when the electron distribution function possesses the Maxwellian, Druyvestein or Kappa functional forms, kinetic and thermodynamic electron temperatures yield the same value.

The growth of nanostructured physical vapor deposited thin films at oblique angles is becoming a hot topic for the development of a large variety of applications. Up to now, empirical relations, such as the so-called tangent rule, have been uncritically applied to account for the development of the nanostructure of these thin films even when they do not accurately reproduce most experimental results. In the present paper, the growth of thin films at oblique angles is analyzed under the premises of a recently proposed surface trapping mechanism. The authors demonstrate that this process mediates the effective shadowing area and determines the relation between the incident angle of the deposition flux and the tilt angle of the columnar thin film nanostructures. The analysis of experimental data for a large variety of materials obtained in our laboratory and taken from the literature supports the existence of a connection between the surface trapping efficiency and the metallic character of the deposited materials. The implications of these predictive conclusions for the development of new applications based on oblique angle deposited thin films are discussed.

The formation of the porous structure in dc magnetron sputtered amorphous silicon thin films at low temperatures is studied when using helium and/or argon as the processing gas. In each case, a-Si thin films were simultaneously grown at two different locations in the reactor which led to the assembly of different porous structures. The set of four fabricated samples has been analyzed at the microstructural level to elucidate the characteristics of the porous structure under the different deposition conditions. With the help of a growth model, we conclude that the chemical nature of the sputter gas not only affects the sputtering mechanism of Si atoms from the target and their subsequent transport in the gaseous/plasma phase towards the film, but also the pore formation mechanism and dynamics. When Ar is used, pores emerge as a direct result of the shadowing processes of Si atoms, in agreement with Thornton's structure zone model. The introduction of He produces, in addition to the shadowing effects, a new process where a degree of mobility results in the coarsening of small pores. Our results also highlight the influence of the composition of sputtering gas and tilt angles (for oblique angle deposition) on the formation of open and/or occluded porosity

In the last few years, several papers have appeared showing the capabilities of electron Rutherford backscattering spectrometry (eRBS) to quantify the H content at surfaces. The basis of the H detection in this technique relies on the difference in recoil energy of the incident electrons depending on the mass of the atoms located at the surface that act as scatter centers. In this paper, we address the interpretation of eRBS spectra of hydrogen containing surfaces. The aim is to compare the naïve single elastic scattering approximation with a more realistic description of eRBS spectra including multiple elastic scattering using the HQ-eRBS (hydrogen quantification eRBS) software based on a Monte Carlo algorithm. It is concluded that multiple elastic scattering is a significant contribution to experimentally measured eRBS spectra of a polyethylene surface. It induces significant broadening of the distribution of the maximum elastic scattering angle along the electron trajectories contributing to the measured spectra. However, it has weak effect in the energy distribution of the collected electrons (about 10% overestimation of the H content in the particular case of a polyethylene surface with respect to the corresponding ratio of elastic scattering cross sections

Growth regimes of gold thin films deposited by magnetron sputtering at oblique angles and low temperatures are studied from both theoretical and experimental points of view. Thin films were deposited in a broad range of experimental conditions by varying the substrate tilt angle and background pressure, and were analyzed by Field Emission Scanning Electron Microscopy (FESEM) and Grazing Incidence Small-Angle X-ray Scattering (GISAXS) techniques. Results indicate that the morphological features of the films strongly depend on the experimental conditions, but can be categorized within four generic microstructures, each of them defined by different bulk geometrical patterns and pore percolation depth and connectivity. With the help of a growth model, a microstructure phase diagram has been constructed where the main features of the films are depicted as a function of experimentally controllable quantities, finding a good agreement with the experimental results in all the studied cases.

In the present work we have investigated the relationships existing between the optical properties and the growth mechanism, microstructure and surface roughness of SnO2 and ZnO oxide films prepared by magnetron sputtering under conditions resembling those utilized in industry. Thin films of these oxides with different thicknesses were characterized by atomic force microscopy, glancing incidence X-ray diffraction (GIXRD), X-ray reflectometry and spectroscopic ellipsometry. The roughness evolution of the film properties (density, surface roughness and refraction index) as a function of their thickness has been evaluated within the concepts of the Dynamic Scaling Theory of thin film growth. Zinc oxide films were rougher than tin oxide films of similar thickness, indicating a different growing mechanism for the two materials. Silver was evaporated onto the surface of the two oxide thin films and its earlier stages of nucleation studied by background analysis of the X-ray photoemission spectra. A different nucleation mechanism was found depending on the nature of the oxide acting as substrate. The superior performance of the zinc oxide based low emissive coatings is related with a better wetting of silver on the surface of this oxide despite the comparatively lower roughness of the tin oxide layers.

Growth of amorphous SiO2 thin films deposited by reactive magnetron sputtering at low temperatures has been studied under different oxygen partial pressure conditions. Film microstructures varied from coalescent vertical column-like to homogeneous compact microstructures, possessing all similar refractive indexes. A discussion on the process responsible for the different microstructures is carried out focusing on the influence of (i) the surface shadowing mechanism, (ii) the positive ion impingement on the film, and (iii) the negative ion impingement. We conclude that only the trend followed by the latter and, in particular, the impingement of O- ions with kinetic energies between 20 and 200 eV, agrees with the resulting microstructural changes. Overall, it is also demonstrated that there are two main microstructuring regimes in the growth of amorphous SiO2 thin films by magnetron sputtering at low temperatures, controlled by the amount of O2 in the deposition reactor, which stem from the competition between surface shadowing and ion-induced adatom surface mobility

The microstructural features of amorphous TiO2 thin films grown by the electron beam physical vapour deposition technique at oblique angles have been experimentally and theoretically studied. The microstructural features of the deposited films were characterized by considering both, the column tilt angle and the increase of the column thickness with height. A Monte Carlo model of the film growth has been developed that takes into account surface shadowing, short-range interaction between the deposition species and the film surface, as well as the angular broadening of the deposition flux when arriving at the substrate. The good match between simulations and experimental results indicates the importance of these factors in the growth and microstructural development of thin films deposited at oblique angles.

The influence of isotropically directed deposition flux on the formation of the thin film microstructure at low temperatures is studied. For this purpose we have deposited TiO2 thin films by two different deposition techniques: reactive magnetron sputtering, in two different experimental configurations, and plasma enhanced chemical vapor deposition. The obtained results indicate that films grown under conditions where deposition particles do not possess a clear directionality, and in the absence of a relevant plasma/film interaction, present similar refractive indices no matter the deposition technique employed. The film morphology is also similar and consists of a granular surface topography and a columnarlike structure in the bulk whose diameter increases almost linearly with the film thickness. The deposition has been simulated by means of a Monte Carlo model, taking into account the main processes during growth. The agreement between simulations and experimental results indicates that the obtained microstructures are a consequence of the incorporation of low-energy, isotropically directed, deposition particles.

We show that the tilt angle of nanostructures obtained by glancing angle sputtering is finely tuned by selecting the adequate argon pressure. At low pressures, a ballistic deposition regime dominates, yielding high directional atoms that form tilted nanocolumns. High pressures lead to a diffusive regime which gives rise to vertical columnar growth. Monte Carlo simulations reproduce the experimental results indicating that the loss of directionality of the sputtered particles in the gas phase, together with the self-shadowing mechanism at the surface, are the main processes responsible for the development of the columns.

Morphological evolution of ZrO2 thin films deposited during pulsed laser deposition of Zr in O2 atmosphere has been experimentally studied at two different film deposition temperatures, 300 and 873 K. The roughness exponent, , the growth exponent, , the coarsening exponent, 1/z, and the exponent defining the evolution of the characteristic wavelength of the surface, p, for depositions at 300 K amounted to = 1.00.1, = 0.40.1, 1/z= 0.340.03, and p= 0.490.03, whereas for depositions carried out at 873 K amounted to = 0.30.3, = 0.40.2, and 1/z= 0.00.2. Experimental error becomes important due to the flat morphology of the films inherent to the deposition technique. The change in the surface topography with the film temperature has been studied with the help of a simple Monte Carlo model which indicates the existence of two different growth regimes: a shadowing dominated growth, occurring at low temperatures, characterized by calculated values = 1.000.04, = 0.500.04, p= 0.460.01, and 1/z= 0.350.02 and a diffusion dominated growth that takes place at high temperatures as well as at low deposition rates, characterized by calculated values = 0.150.08, = 0.330.04, and 1/z= 0.330.07. The good agreement obtained between the experimental and simulated parameters is discussed within the frame of the general characteristics of the deposition method.