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.

Metallurgical coatings 1988 is a compilation of the proceedings of the 15th International Conference on Metallurgical Coatings. This volume is divided into four parts, which deal with synthesis and properties of coatings used in microelectronic applications; methods of characterizing coatings and modified surfaces; protective coatings for magnetic and optical thin film media; and thick and thin film censors. The first part of this volume is further subdivided into five sections focusing on thin film barrier layers, metallization for VLSI circuits, thin films used in packaging technology, new materials and emerging technologies and synthesis and microstructure of high Tc superconductors. The second part is also subdivided into four sections, each presenting different methods, such as the surface and thin film analysis techniques, microstructural characterization techniques, mechanical properties of films and coatings, and non-destructive characterization techniques. Part three discusses the preparation and characterization of reactively sputtered silicon nitride thin films, the bond structures and properties of chemically vapor-deposited amorphous SiC, and the wear of Co-Ni thin film magnetic recording tape against metallic and ceramic surfaces. Finally, this volume explores the insert-mounted thin film sensors for real-time.

This second edition, edited by the world-renowned Dr. Rointain Bunshah, is an extensive update of the many improvements in deposition technologies, mechanisms, and applications. Considerably more material was added in Plasma Assisted Vapor Deposition processes, as well as Metallurgical Coating Applications.