Transition films from amorphous (a-) to microcrystalline (μc-) silicon were prepared by hot-wire chemical vapor deposition using silane decomposition with either varied hydrogen-to-silane ratio, R, or with fixed R=3 but a varied substrate temperature, Ts. Raman results indicate that there is a threshold for the structural transition from a- to μc-Si:H in both cases. The onset of the structural transition is found to be R≈2 at Ts=250 °C and Ts≈200 °C at R=3. The properties of the material were studied by infrared absorption, optical absorption, photoluminescence (PL), and conductivity temperature dependence. We observed that the peak frequency of the SiH wag mode remains at 630-640 cm-1 for all the films, but the hydrogen content shows two regimes of fast and slow decreases separated by the onset of microcrystallinity. When microcrystallinity increased, we observed that (a) the SiO vibration absorption at 750 cm-1 and 1050-1200 cm-1 appeared, (b) the relative intensity of the 2090 cm-1 absorption increased, (c) the low-energy optical absorption at photon energy ≪1.4 eV increased one to two orders of magnitude, (d) the low-energy PL band at ∼1.0 eV emerged with a decrease of total PL intensity, and (e) the conductivity activation energy decreased. The aforementioned changes correlated well with the crystallinity of the material. We attribute the observations mainly- to the formation of the c-Si gain boundaries during crystallization. © 2003 American Institute of Physics.