Crystalline thin films of silicon nitride have been grown on a variety of substrates by microwave plasma-enhanced chemical vapor deposition using N2, O2, and CH4 gases at a temperature of 800 deg C. X-ray diffraction and Rutherford backscattering measurements indicate the deposits are stoichiometric silicon nitride with varying amounts of the alpha and beta phases. Scanning electron microscope imaging indicates beta-Si3N4 possesses six-fold symmetry with particles size in the submicron range. In one experiment, the silicon necessary for growth comes from the single crystal silicon substrate due to etching/sputtering by the nitrogen plasma. The dependence of the grain size on the methane concentration is investigated. In an another experiment, an organo- silicon source, methoxytrimethylsilane, is used to grow silicon nitride with controlled introduction of the silicon necessary for growth. Thin crystalline films are deposited at rates of 0.1 micrometer/hr as determined by profilometry. A growth mechanism for both cases is proposed.

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.