New halo-carbon precursor, CH3Cl, is used in this work to replace the traditional C3H8 gas as a carbon precursor for the homoepitaxial growth of 4H-SiC. The traditional SiH4-C3H8-H2 systems require high growth temperatures to enable the desirable steplow growth for high-quality epilayers. A well known problem of the regular-temperature growth is the homogeneous gas-phase nucleation caused by SiH4 decomposition. However, the degree of Si cluster formation in the gas phase and its influence on our low-temperature epitaxial growth was unknown prior to this work. Growth at temperatures below 1400°C was demonstrated previously only for a limited range of substrate surface orientations and with poor quality. Mirror-like epilayer surface without foreign polytype inclusions and with rare surface defects was demonstrated at temperatures down to 1280-1300°C for our halo-carbon growth. Quantitatively different growth-rate dependences on the carbon-precursor flow rate suggested different precursor decomposition kinetics and different surface reactions in CH3Cl and C3H8 systems. Photoluminescence measurement indicated the high quality of the epilayers grown at 1300°C. A mirror-like surface morphology with rare surface defects was demonstrated for the growth on low off-axis substrates at 1380°C. The most critical growth-rate limiting mechanism during the low-temperature epitaxial growth is the formation of Si clusters, which depleted the Si supply to the growth surface, in the gas phase. Presence of chlorine in the CH3Cl precursor significantly reduces but does not completely eliminate this problem. The addition of HCl during growths improved the growth rate and surface morphology drastically but also brought up some complex results, suggesting more complex mechanisms of HCl interaction with the gas-phase clusters. These complicated results were explained partly by an additional mechanism of precursor depletion enhanced in presence of HCl. Complex changes in the effective silicon to carbon ratio in the growth zone indicated that the supply of carbon species may also be enhanced at least at low HCl flow rates. This fact allowed us to suggest that the gas-phase clusters may contain a significant amount of carbon. The new model assuming coexistence of the silicon and carbon in the gas-phase clusters enabled the explanation of the complex experimental trends reported in this work.

<p>SiC is an attractive material since it has remarkable properties. For several years efforts have been put primarily in electronic applications. High power and high frequency devices can be fabricated on SiC due to its wide band gap, high breakdown field and high thermal conductivity. SiC devices can be used in harsh environment since its operation temperature is significantly high (about 1200 ). SiC bulk growth has been improved by seeded physical vapour transport (PVT) during last decades. However, the quality and doping concentration of SiC bulk are not good enough to be used as an active layer for devices. SiC epilayer growth by chemical vapour deposition (CVD) was established in the last three decades. Only about 5 µm/h growth rate is achieved by CVD with a standard process. Long deposition time is required to grow ≥100µm thick epilayer for high voltage devices. The main problem in standard CVD is the formation of silicon (Si) droplets due to supersaturation of Si-species on the growth surface or in the gas-phase, which is detrimental for devices performance. To solve the problem of Si-droplets, chloride-based CVD was introduced. Chlorinated species can dissolve the silicon aggregates through the formation of strong bonds to silicon species compared to Si-Si bonds. Typical chlorinated precursors are hydrogen chloride (HCl) and methyltrichlorosilane (MTS). In this thesis study, HCl was mainly used as chlorinated precursors. Distinct chlorinated precursors result in different chemical reactions which affect the epilayer growth appreciably. The Cl/Si ratio, which is the ratio of the amount of chlorinated precursors to silicon precursors, is a very critical growth parameter for morphology, growth rate and background doping concentration. The C/Si ratio and Si/H₂ ratio also affect the epilayer growth appreciably. Besides, growth temperature, growth pressure and temperature ramp up condition are other important growth parameters. In the CVD reaction chamber, the temperature profile and gas species distribution are not uniform along the whole susceptor length, which leads to different thickness of epilayer, morphology and doping concentration at different area of the reaction chamber. The polarity and off-angle of substrates can bring about complete different grown epilayers. Epitaxial defects are mainly replicated from the substrate. Therefore, the quality of substrates is very important as well. Deep energy levels can be introduced by adding transition metal such as vanadium (V), chromium (Cr) or tungsten (W). There are some limits which are needed to be overcome for a complete development of SiC. 4” SiC wafers are commercially available on the market, larger diameter would be very useful for the industrial development of SiC. High growth rate and good quality with controlled uniformity are desired for electronic applications. In this thesis, the influences of growth parameters such as C/Si and Cl/Si ratios, comparison between different precursors, growth condition in different areas of reaction chamber and effects of substrate polarity are discussed. Intentional incorporation of tungsten atoms is investigated by deep-level transient spectroscopy measurement and thermodynamic analysis.</p>

SiC is an attractive material since it has remarkable properties. For several years efforts have been put primarily in electronic applications. High power and high frequency devices can be fabricated on SiC due to its wide band gap, high breakdown field and high thermal conductivity. SiC devices can be used in harsh environment since its operation temperature is significantly high (about 1200 ). SiC bulk growth has been improved by seeded physical vapour transport (PVT) during last decades. However, the quality and doping concentration of SiC bulk are not good enough to be used as an active layer for devices. SiC epilayer growth by chemical vapour deposition (CVD) was established in the last three decades. Only about 5 µm/h growth rate is achieved by CVD with a standard process. Long deposition time is required to grow ≥100µm thick epilayer for high voltage devices. The main problem in standard CVD is the formation of silicon (Si) droplets due to supersaturation of Si-species on the growth surface or in the gas-phase, which is detrimental for devices performance. To solve the problem of Si-droplets, chloride-based CVD was introduced. Chlorinated species can dissolve the silicon aggregates through the formation of strong bonds to silicon species compared to Si-Si bonds. Typical chlorinated precursors are hydrogen chloride (HCl) and methyltrichlorosilane (MTS). In this thesis study, HCl was mainly used as chlorinated precursors. Distinct chlorinated precursors result in different chemical reactions which affect the epilayer growth appreciably. The Cl/Si ratio, which is the ratio of the amount of chlorinated precursors to silicon precursors, is a very critical growth parameter for morphology, growth rate and background doping concentration. The C/Si ratio and Si/H2 ratio also affect the epilayer growth appreciably. Besides, growth temperature, growth pressure and temperature ramp up condition are other important growth parameters. In the CVD reaction chamber, the temperature profile and gas species distribution are not uniform along the whole susceptor length, which leads to different thickness of epilayer, morphology and doping concentration at different area of the reaction chamber. The polarity and off-angle of substrates can bring about complete different grown epilayers. Epitaxial defects are mainly replicated from the substrate. Therefore, the quality of substrates is very important as well. Deep energy levels can be introduced by adding transition metal such as vanadium (V), chromium (Cr) or tungsten (W). There are some limits which are needed to be overcome for a complete development of SiC. 4” SiC wafers are commercially available on the market, larger diameter would be very useful for the industrial development of SiC. High growth rate and good quality with controlled uniformity are desired for electronic applications. In this thesis, the influences of growth parameters such as C/Si and Cl/Si ratios, comparison between different precursors, growth condition in different areas of reaction chamber and effects of substrate polarity are discussed. Intentional incorporation of tungsten atoms is investigated by deep-level transient spectroscopy measurement and thermodynamic analysis.