Abstract: The present invention relates to a method of manufacturing a photovoltaic device having an ultra-shallow junction layer. In the method, a crystalline silicon substrate is cleaned and a first doped semiconductor layer with 1.12 eV bandgap and 5˜80 nm of thickness is grown on the crystalline silicon substrate by high density plasma electron cyclotron resonance CVD in a preparation condition of a temperature of the crystalline silicon substrate ranging from 50° C. to 250° C. , about 500W of microwave power, deposition pressure below 50 mTorr, about 20 sccm of argon and hydrogen flow rate, SiH4 flow rate ranging from 1 sccm to 2 sccm, and 2% boroethane flow rate ranging from about 5 seem to 15 sccm. The photovoltaic device of the present invention has advantages of abrupt homo-junction, ultra-thin high-crystallinity silicon-based thin film, highly-doped concentration, high conductivity and high short-circuit current, thereby having improved efficiency.