We have applied real-time spectroscopic ellipsometry (RTSE) as both an in-situ diagnostic and post-growth analysis tool for hydrogenated amorphous silicon (a-Si:H)/crystalline silicon (c-Si) heterojunction with intrinsic thin-layer (HIT) solar cells grown by hot-wire chemical vapor deposition. RTSE enables precise thickness control of the 5 to 25 nm layers used in these devices, as well as monitoring crystallinity and surface roughness in real time. Utilizing RTSE feedback, but without extensive optimization, we have achieved a photovoltaic energy conversion efficiency of 14.1% on an Al-backed p-type Czochralski c-Si wafer coated with thin i and n layers on the front. Open-circuit voltages above 620 mV indicate effective passivation of the c-Si surface by the a-Si:H intrinsic layer. Lifetime measurements using resonant coupled photoconductive decay indicate that surface recombination velocities can approach 1 cm/s. RTSE and transmission electron microscopy show that the intrinsic a-Si:H i-layers grow as a mixture of amorphous and nano-crystalline silicon.