The oblique angle configuration has emerged as an invaluable tool for the deposition of nanostructured thin films. This review develops an up to date description of its principles, including the atomistic mechanisms governing film growth and nanostructuration possibilities, as well as a comprehensive description of the applications benefiting from its incorporation in actual devices. In contrast with other reviews on the subject, the electron beam assisted evaporation technique is analyzed along with other methods operating at oblique angles, including, among others, magnetron sputtering and pulsed laser or ion beam-assisted deposition techniques. To account for the existing differences between deposition in vacuum or in the presence of a plasma, mechanistic simulations are critically revised, discussing well-established paradigms such as the tangent or cosine rules, and proposing new models that explain the growth of tilted porous nanostructures. In the second part, we present an extensive description of applications wherein oblique-angle-deposited thin films are of relevance. From there, we proceed by considering the requirements of a large number of functional devices in which these films are currently being utilized (e.g., solar cells, Li batteries, electrochromic glasses, biomaterials, sensors, etc.), and subsequently describe how and why these nanostructured materials meet with these needs.Peer reviewe

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 and grazing-incidence small-angle x-ray scattering 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 a different bulk geometrical pattern, 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.

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.

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.

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.