Electrochemical Deposition of Silicon: A Critical Review of Electrolyte Systems for Industrial Implementation

Electrochemical deposition of silicon is considered a promising alternative to conventional high-temperature and high-emission methods of silicon production. This review analyzes the current state of research on electrolyte systems used for silicon electrodeposition, with a particular focus on their potential for industrial-scale application. These systems are evaluated based on key characteristics relevant to such implementation, including silicon precursor solubility, electrical conductivity, applicable current density, and behavior under process conditions. The study evaluates fluoride-based, chloride-based, mixed halide, and organic electrolyte systems based on key criteria, including conductivity, chemical stability, silicon precursor solubility, temperature range, and ease of product purification. Fluoride-based melts offer high current densities (up to 2 A/cm²) and effective SiO₂ dissolution but operate at high temperatures (550-1300 °C) and suffer from hygroscopicity. Chloride systems exhibit lower operating temperatures (300-1000 °C) and better water solubility but lack compatibility with common silicon sources. Mixed fluoride-chloride electrolytes emerge as the most promising option, combining high performance with improved practicality; they operate at 600-850 °C and current densities up to ~1.5 A/cm². Additional focus is placed on the impact of substrate materials and on unresolved questions related to reaction reversibility, kinetic mechanisms, and the influence of electrolyte composition. The review concludes that further fundamental studies are needed to optimize electrolyte design and enable the transition from laboratory-scale research to industrial implementation.