Challenges in the Synthesis and Processing of Hydrosilanes as Precursors for Silicon Deposition

Hydrosilanes are highly attractive compounds, which can be processed as liquids with printing technology to amorphous silicon films on nearly any solid substrate. The silicon layers can be processed for electronic devices like transistors or thin-film solar cells. The endothermic character of hydrosilanes with their positive enthalpies of formation results in favorable properties for processing. The larger the molecules, the lower their decomposition temperature and the higher their photoactivity. Cyclic hydrosilanes such as cyclopentasilane and cyclohexasilane can be easily deposited. The branched neopentasilane is more difficult to deposit but yields better-quality films after processing. The key challenge is the complex synthesis of the precursors and the hydrosilanes. The available preparative methods are presented in this review and their advantages and disadvantages are evaluated. The following synthesis methods are presented and discussed in this article: Wurtz coupling and other reductive coupling processes, dehydrogenative coupling of silanes, plasma synthesis of chlorinated polysilanes, amine- or chloride-induced disproportionations, and transformation of monosilane to higher silanes. Plasma synthesis is already carried out today as a continuous industrial process. The most effective synthesis methods in the laboratory are currently amine- and chloride-induced disproportionations. There is a great need to further optimize the syntheses of hydrosilanes and to develop new simple synthesis variants.