Hydrosilane Chemistry: From Historic First Steps to Modern Applications

The chemistry of hydrosilanes has seen a significant resurgence, driven by novel applications in printed electronics and solar cells. This review provides a historical account of hydrosilanes, from their early discoveries to modern advancements. The narrative begins with the initial synthesis of monosilane and the foundational work of Alfred Stock, who developed crucial techniques for handling these sensitive compounds and characterized a range of linear and functionalized silanes. This is followed by a period of significant advancement, led by Franz Fehér, optimized synthesis methods and expanded the scope to higher, branched, and functionalized silanes. The paper also covers the development of hydrogen‐substituted silicon polymers and the available syntheses of hydrosilanes. Recent advances in hydrosilane synthesis, including disproportionation of perchlorosilanes and coupling of silanides, are highlighted. A key focus is the recent, groundbreaking use of liquid hydrosilanes as “silicon ink,” which enables the low‐temperature deposition of silicon films for thin‐film transistors and other electronic devices. The review concludes by considering future trends for this versatile class of compounds.