A number of thin silicon films are deposited on crystalline silicon, native oxidized crystalline silicon, and optical quality fused quartz substrates through the use of ultra-high-vacuum evaporation at growth temperatures ranging from 98 to 572 °C. An analysis of their grazing incidence X-ray diffraction and Raman spectra indicates that a phase transition, from amorphous-to-crystalline, occurs as the growth temperature is increased. Through a peak decomposition process, applied to the Raman spectroscopy results, the crystalline volume fractions associated with these samples are plotted as a function of the growth temperature for the different substrates considered. It is noted that the samples grown on the crystalline silicon substrates have the lowest crystallanity onset temperature, whereas those grown on the optical quality fused quartz substrates have the highest crystallanity onset temperature; the samples grown on the native oxidized crystalline silicon substrates have a crystallanity onset temperature between these two limits. These resultant dependencies on the growth temperature provide a quantitative means of characterizing the amorphous-to-crystalline phase transition within these thin silicon films. It is noted that the thin silicon film grown on an optical quality fused quartz substrate at 572 °C, possessing an 83% crystalline volume fraction, exhibits an optical absorption spectrum which is quite distinct from that associated with the other thin silicon films. We suggest that this is due to the onset of sufficient long-range order in the film for wave-vector conservation to apply, at least partially. Finally, we use a semi-classical optical absorption analysis to study how this phase transition, from amorphous-to-crystalline, impacts the spectral dependence of the optical absorption coefficient.