Doped polysilanes, inks containing the same, and methods for their preparation and use are disclosed. The doped polysilane generally has the formula H-[AaHb(DRx)m]q-[(AcHdR1e)n]p—H, where each instance of A is independently Si or Ge, and D is B, P, As or Sb. In preferred embodiments, R is H, -AfHf+1R2f, alkyl, aryl or substituted aryl, and R1 is independently H, halogen, aryl or substituted aryl. In one aspect, the method of making a doped poly(aryl)silane generally includes the steps of combining a doped silane of the formula AaHb+2(DRx)m (optionally further including a silane of the formula AcHd+2R1e) with a catalyst of the formula R4wR5yMXz (or an immobilized derivative thereof) to form a doped poly(aryl)silane, then removing the metal M. In another aspect, the method of making a doped polysilane includes the steps of halogenating a doped polyarylsilane, and reducing the doped halopolysilane with a metal hydride to form the doped polysilane. The synthesis of semiconductor inks via dehydrocoupling of doped silanes and/or germanes allows for tuning of the ink properties (e.g., viscosity, boiling point, surface tension and dopant level or concentration) and for deposition of doped silicon films or islands by spincoating, inkjetting, dropcasting, etc., with or without the use of UV irradiation.