Pristine polysilane containing only Si and H is considered as a potential precursor material that allows the solution-based deposition of hydrogenated amorphous Si (a-Si:H) thin-films reducing manufacturing cost of Si thin-film photovoltaic devices. This study explored three different synthetic routes including Wiirtz-type reductive coupling reaction, hydrogenation of Si anionic compound, and the dehydrocoupling reaction in order to realize the soluble polysilane molecules. While Wiirtz-type reaction of diiodosilane presented us a direct synthetic scheme for hydrogenated polysilane, the results indicated that an extremely controlled air-free system for the synthesis and sample handling would be necessary to prevent the formation of siloxane bonds from the spontaneous reaction between silane-based molecules and water in the air. While the hydrogenation of CaSi2 and the dehydrocoupling reaction of phenylsilane provided more stable forms of polysilane, dissolution of the polysilane from CaSi2 in dichlorobenzene was not successful possibly due to its layered structure succeeded from CaSi2 and the removal of the phenyl groups from the synthesized polyphenylsilane remains as a challenge to realize the polysilane precursor necessary for the solution-based thin-film process of a-Si:H. (C) 2011 Elsevier B.V. All rights reserved.