Silicon nitride and silicon nitride-based ceramics have several favorable material properties, such as high hardness and good wear resistance, which makes them important materials for the coating industry. This thesis focuses the synthesis of silicon nitride, silicon oxynitride, and silicon carbonitride thin films by reactive magnetron sputtering. The films were characterized based on their chemical composition, chemical bonding structure, and mechanical properties to link the growth conditions to the film properties. Silicon nitride films were synthesized by reactive high power impulse magnetron sputtering (HiPIMS) from a Si target in Ar/N2 atmospheres, whereas silicon oxynitride films were grown by using nitrous oxide as the reactive gas. Silicon carbonitride was synthesized by two different methods. The first method was using acetylene (C2H2) in addition to N2 in a Si HiPIMS process and the other was co-sputtering of Si and C, using HiPIMS for Si and direct current magnetron sputtering (DCMS) for graphite targets in an Ar/N2 atmosphere. Langmuir probe measurements were carried out for the silicon nitride and silicon oxynitride processes and positive ion mass spectrometry for the silicon nitride processes to gain further understanding on the plasma conditions during film growth. The target current and voltage waveforms of the reactive HiPIMS processes were evaluated. The main deposition parameter affecting the nitrogen concentration of silicon nitride films was found to be the nitrogen content in the plasma. Films with nitrogen contents of 50 at.% were deposited at N2/Ar flow ratios of 0.3 and above. These films showed Si-N as the dominating component in Si 2p X-ray photoelectron spectroscopy (XPS) core level spectra and Si–Si bonds were absent. The substrate temperature and target power were found to affect the nitrogen content to a lower extent. The residual stress and hardness of the films were found to increase with the film nitrogen content. Another factors influencing the coating stress were the process pressure, negative substrate bias, substrate temperature, and HiPIMS pulse energy. Silicon nitride coatings with good adhesion and low levels of compressive residual stress were grown by using a pressure of 600 mPa, a substrate temperature below 200 °C, pulse energies below 2.5 Ws, and negative bias voltages up to 100 V. The elemental composition of silicon oxynitride films was shown to depend on the target power settings as well as on the nitrous oxide flow rate. Silicon oxide-like films were synthesized under poisoned target surface conditions, whereas films deposited in the transition regime between poisoned and metallic conditions showed higher nitrogen concentrations. The nitrogen content of the films deposited in the transition region was controlled by the applied gas flow rate. The applied target power did not affect the nitrogen concentration in the transition regime, while the oxygen content increased at decreasing target powers. The chemical composition of the films was shown to range from silicon-rich to effectively stoichiometric silicon oxynitrides, where no Si–Si contributions were found in the XPS Si 2p core level spectra. The film optical properties, namely the refractive index and extinction coefficient, were shown to depend on the film chemical bonding, with the stoichiometric films displaying optical properties falling between those of silicon oxide and silicon nitride. The properties of silicon carbonitride films were greatly influenced by the synthesis method. The films deposited by HiPIMS using acetylene as the carbon source showed silicon nitride-like mechanical properties, such as a hardness of ~ 20 GPa and compressive residual stresses of 1.7 – 1.9 GPa, up to film carbon contents of 30 at.%. At larger film carbon contents the films had increasingly amorphous carbon-like properties, such as densities below 2 g/cm3 and hardnesses below 10 GPa. The films with more than 30 at.% carbon also showed columnar morphologies in cross-sectional scanning electron microscopy, whereas films with lower carbon content showed dense morphologies. Due to the use of acetylene the carbonitride films contained hydrogen, up to ~ 15 at.%. The co-sputtered silicon carbonitride films showed a layered SiNx/CNx structure. The hardness of these films increased with the film carbon content, reaching a maximum of 18 GPa at a film carbon content of 12 at.%. Comparatively hard and low stressed films were grown by co-sputtering using a C target power of 1200 W for a C content around 12 at.%, a negative substrate bias less than 100 V, and a substrate temperature up to 340 °C.

A variety of nanomaterials have excellent optoelectronic and electronic properties for novel device applications. At the same time, and with advances in silicon integrated circuit (IC) techniques, compatible Si-based nanomaterials hold promise of applying the advantages of nanomaterials to the conventional IC industry. This book focuses not only on silicon nanomaterials, but also summarizes up-to-date developments in the integration of non-silicon nanomaterials on silicon. The book showcases the work of leading researchers from around the world who address such key questions as: Which silicon nanomaterials can give the desired optical, electrical, and structural properties, and how are they prepared? What nanomaterials can be integrated on to a silicon substrate and how is this accomplished? What Si-based nanomaterials may bring a breakthrough in this field? These questions address the practical issues associated with the development of nanomaterial-based devices in applications areas such as solar cells, luminous devices for optical communication (detectors, lasers), and high mobility transistors. Investigation of silicon-based nanostructures is of great importance to make full use of nanomaterials for device applications. Readers will receive a comprehensive view of Si-based nanomaterials, which will hopefully stimulate interest in developing novel nanostructures or techniques to satisfy the requirements of high performance device applications. The goal is to make nanomaterials the main constituents of the high performance devices of the future.

The book covers very important issues, not only scientific in nature but, ultimately, for industry and the economy. Wear and deterioration of surface properties during operation is a natural and unavoidable phenomenon. However, minimizing the degree of wear is of great importance for the entire economy, as illustrated by the example of the US economy, for which the loss of natural resources as a direct cause of friction and wear exceeds 6% of the Gross National Product. This book showcases the valuable knowledge revealed from both theoretical and practical research results in the field of advanced technologies of coatings and surface modification, as well as wear and tribological characteristics of advanced materials and surface layers. Therefore, it is hoped that this book will be a valuable resource and helpful tool for scientists, engineers, and students in the field of surface engineering, materials science, and manufacturing engineering.

This book delivers practical insight into a broad range of fields related to hard coatings, from their deposition and characterization up to the hardening and deformation mechanisms allowing the interpretation of results. The text examines relationships between structure/microstructure and mechanical properties from fundamental concepts, through types of coatings, to characterization techniques. The authors explore the search for coatings that can satisfy the criteria for successful implementation in real mechanical applications.

Recent years have witnessed the flourishing of numerous novel strategies based on the magnetron sputtering technique aimed at the advanced engineering of thin films, such as HiPIMS, combined vacuum processes, the implementation of complex precursor gases or the inclusion of particle guns in the reactor, among others. At the forefront of these approaches, investigations focused on nanostructured coatings appear today as one of the priorities in many scientific and technological communities: The science behind them appears in most of the cases as a "terra incognita", fascinating both the fundamentalist, who imagines new concepts, and the experimenter, who is able to create and study new films with as of yet unprecedented performances. These scientific and technological challenges, along with the existence of numerous scientific issues that have yet to be clarified in classical magnetron sputtering depositions (e.g., process control and stability, nanostructuration mechanisms, connection between film morphology and properties or upscaling procedures from the laboratory to industrial scales) have motivated us to edit a specialized volume containing the state-of-the art that put together these innovative fundamental and applied research topics. These include, but are not limited to: • Nanostructure-related properties; • Atomistic processes during film growth; • Process control, process stability, and in situ diagnostics; • Fundamentals and applications of HiPIMS; • Thin film nanostructuration phenomena; • Tribological, anticorrosion, and mechanical properties; • Combined procedures based on the magnetron sputtering technique; • Industrial applications; • Devices.

Nanocomposite materials as a special class of nanostructured materials have recently attracted great interest due to their extraordinary mechanical properties as well as thermal stability and oxidation resistance. The unique structure and exceptional properties make nanocomposite materials a possible alternative to traditional polycrystalline materials, which have met their limits in many recent engineering applications. In particular, nanocomposite coatings synthesized by plasma-assisted deposition processes under highly non-equilibrium conditions provide a high potential for new applications as protective and functional coatings in automotive, aerospace, tooling, electronic, or manufacturing industry. This book provides a comprehensive overview of the synthesis of Si-containing hard nanocomposite coatings based on transition metal nitrides by plasma-based thin film processing. It demonstrates the full versatility of these nanocomposites for low Si-containing coatings tailored with superior mechanical properties and novel high Si-containing nanocomposite coatings with extraordinary thermal stability and resistance against oxidation optimized for high-temperature applications. It pays special attention to understanding growth mechanisms of these structures under specific deposition conditions, structure–property relations, and stability of individual constituents to enhance their functionality for various applications.