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State-of-the-art solar-grade silicon production is energy intensive and has a negative impact on the environment. Due to the robust and rapid growth of the Si-based photovoltaic (PV) industry, it is necessary to develop a greener technology for silicon production. Solid oxide membrane (SOM) electrolysis is a proven versatile green technology that can be developed to economically produce many important metal or metal compounds from their oxides. This work will discuss application of SOM electrolysis to produce solar-grade silicon from silica in a single-step resulting in net-zero-carbon emission. The high-temperature SOM electrolysis cell employs stable molten oxide-fluoride bath with silicon wafer cathode and stabilized zirconia membrane-based novel anodes. The cell design and process parameters are selected to enable silicon deposition on the Si wafer cathode. However, initially an electrochemical oxidation reaction occurred between silicon and oxygen that involved the cathode/flux/gas interfaces. An approach to successfully prevent this side reaction has been demonstrated. Electrochemical characterization of the SOM process is presented, and post-experimental characterization demonstrates Si deposits in the form of silicon carbide due to the use of graphite crucible and graphite current collector.