Polysilanes, inks containing the same, and methods for their preparation are disclosed. The polysilane generally has the formula H-[(AHR)n(c-AmHpm-2)q]—H, where each instance of A is independently Si or Ge; R is H, -AaHa+1Ra, halogen, aryl or substituted aryl; (n+a)≧10 if q=0, q≧3 if n=0, and (n+q)≧6 if both n and q≠0; p is 1 or 2; and m is from 3 to 12. In one aspect, the method generally includes the steps of combining a silane compound of the formula AHaR14-a, the formula AkHgR1′h and/or the formula c-AmHpmR1rm with a catalyst of the formula R4xR5yMXz (or an immobilized derivative thereof) to form a poly(aryl)silane; then washing the poly(aryl)silane with an aqueous washing composition and contacting the poly(aryl)silane with an adsorbent to remove the metal M. In another aspect, the method includes the steps of halogenating a polyarylsilane to form a halopolysilane; and reducing the halopolysilane with a metal hydride to form the polysilane. The synthesis of semiconductor inks via dehydrocoupling of silanes and/or germanes allows for tuning of the ink properties (e.g., viscosity, boiling point, and surface tension) and for deposition of silicon films or islands by spincoating, inkjetting, dropcasting, etc., with or without the use of UV irradiation.