a-Si:H films and their n-i-p solar cells were prepared using plasma-enhanced CVD. The samples were prepared with no-, low-, standard, and high-H dilution. Raman and photoluminescence (PL) were used to characterize the i-layer. The main results are (a) Raman shows typical a-Si:H mode except for a c-Si peak in the 450 nm-thick film with high-H dilution, and (b) PL shows two regimes. (I) Below the onset of microcrystallinity characterized by x-ray diffraction, a blue-shift of the 1.4 eV PL peak energy and a decrease of the band width occur. (II) Above the onset of microcrystallinity, the PL efficiency decreases by a factor of 4-5, and the PL peak energy is red-shifted toward 1.2 eV as the μc-Si volume fraction is increased. In addition, the solar cell open circuit voltage shows first an increase and then a decrease, correlating with the PL peak energy position. We conclude that the PL spectroscopy is a sensitive tool for characterizing the gradual amorphous-to-microcrystalline structural transition in thin film solar cells.