Advances in SiC growth using chloride-based CVD

Abstract: Silicon Carbide (SiC) is a wide band-gap semiconductor. Similar to silicon it can be used to make electronic devices which can be employed in several applications. SiC has some unique features, such as wide band-gap, high hardness, chemical inertness, and capability to withstand high temperatures. Its high breakdown electric field, high saturated drift velocity and high thermal conductivity are some of the most important characteristics to understand why SiC has superior electrical properties compared to silicon, and make it very attractive for power devices especially at high voltages and high frequency. The gain in reduced device sizes, reduced cooling requirements, and especially in improved energy efficiency for AC/DC conversion are a very important reasons to keep working in improving the material quality. Yet several issues still limit its full employment in all its potential applications, and many more steps have thus to be done for its complete success.The core of an electric device is the epitaxial layer grown on a substrate by chemical vapor deposition (CVD). Gases containing silicon and carbon atoms, such as silane and ethylene, are often used to grow SiC, but limits in high growth rate are given by silicon cluster formation in the gas phase which is detrimental for the epitaxial layer quality. High growth rates are needed to deposit thick layers ( > 100 μm) which are required for high power devices. Chloride-based CVD, which is usually employed in the silicon epitaxial growth industry, is based on the presence of chlorinated species in the gas mixture which prevent the formation of silicon clusters, therefore resulting in very high growth rates. This chloride-based CVD process was first started to be investigated a few years ago and then only at typical growth conditions, without exploring all its full potential, such as its performance at low or high temperature growth. In addition important parameters affecting the epitaxial layer quality in terms of defect formation and electrical characteristics are the substrate orientation and its off-cut angle. Standard processes are run on substrates having an 8° off-cut angle towards a specific crystallographic direction. On lower off-cut angles, such as 4° or almost 0° (also called on-axis) which would be more economical and could resolve problems related to bipolar degradation, many typical issues should be solved or at least minimized. For 4° off-cut angle the main problem is the step-bunching resulting in high roughness of the epi surface whereas for nominally on-axis the formation of 3C inclusions is the main problem.In this thesis we discuss and present results on the use of the chloride-based CVD process in a hot-wall reactor to further explore most of the above mentioned topics. Onaxis substrates are used to grow homopolytypic epitaxial layers; detailed experiments on the gas phase composition adopting high contents of chlorine made it possible (Paper 1). Optimization of the on-axis surface preparation prior to the growth in combination with a correct choice of chlorinated precursors and growth conditions were required to reach a growth rate of 100 μm/h of 100% 4H polytype (Paper 2). Substrates with a 4° off-cut angle could be grown free from step-bunching, one of the most common morphological issue and usually detrimental for devices. Both the standard and chlorinated-process were successfully used, but at different growth rates (Paper 3). Also for this off-cut substrate a specific surface preparation and selected growth parameters made the growth possible at rates exceeding 100 μm/h (Paper 4). The benefit of the chlorinated chemistry was tested under unusual growth conditions, such as under a concentrated gas mixture (i.e. at very low carrier gas flow) tested on different off-cut substrates (Paper 5). A great advantage of chloride-based chemistry is the feasibility of growing at very low temperatures (1300 to 1400 °C compared to the 1600 °C standard temperature). At such low temperatures 4H-SiC epitaxial layers could be grown on 8° off-axis substrates (Paper 6), while high quality heteroepitaxial 3C-SiC layers were grown on on-axis 6H-SiC substrates (Paper 7). Finally, the very high growth rates achieved by the chloride-based CVD were applied in a vertical hot-wall reactor configuration, demonstrating the ability to grow very thick SiC layers at higher rates and lower temperatures than what is typically used for bulk growth (Paper 8). This work demonstrated that a new bulk growth process could be developed based on this approach.