New insights into the photoassisted anodic reactions of n-type 4H SiC semiconductors

This study aims to investigate the photoelectrochemical behavior of the n-type 4H-SiC, focusing on aqueous, hydroxide-based electrolytes. Despite its high stability, this wide-bandgap semiconductor material undergoes electrochemical reactions, such as anodic oxidation or etching, under specific conditions. Since electrons are the majority charge carriers in n-type semiconductors, oxidation processes require above-bandgap illumination. Then, the reaction rate is influenced by the number of electron holes available for an oxidation process and the velocity of the transport of hydroxide ions to/from the surface. The goal is to focus on the essential reaction parameters (i.e., potential and electrolyte concentration) to clarify the reaction mechanism in aqueous (alkaline) electrolytes. Methods with controllable hydrodynamic conditions are required to investigate the transport processes in the electrolyte. Even though the rotating disk electrode (RDE) is a commonly used and powerful method, it is not well suited for our purpose. Photoelectrochemical etching of SiC is extraordinary because it involves both mass transfer phenomena and gas evolution but also needs high-intensity illumination from an appropriate light source. Hence, a new concept for an inverted rotating cell was developed and implemented. This setup was used to study the effect of the mass transport of hydroxide ions on the photoelectrochemical behavior of SiC in each potential region at varying rotation speeds. In order to interpret the experimental findings, a distinct electrical network model was formulated for simulating the results, aiding in unraveling the underlying reaction mechanism. Electrochemical measurements were complemented by surface-sensitive analytical techniques. XPS was the method of choice to investigate the composition of the sample surface before and after etching. SEM and AFM allow the characterization of the surface morphology in the initial stages of etching. The totality of this information provides a complete picture of the complex processes in the vicinity of the semiconductor electrode.