Hole carrier selective MoOx film is obtained by atomic layer deposition(ALD) using molybdenum hexacarbonyl[Mo(CO)6] as precursor and ozone(O3) oxidant. The growth rate is about 0.036 nm/cycle at 200 g/Nm of ozone concentration and the thickness of interfacial oxide is about 2 nm. The measured band gap and work function of the MoOx film grown by ALD are 3.25 eV and 8 eV, respectively. X-ray photoelectron spectroscopy(XPS) result shows that the Mo6+ state is dominant in the MoOx thin film. In the case of ALD-MoOx grown on Si wafer, the ozone concentration does not affect the passivation performance in the as-deposited state. But, the implied open-circuit voltage increases from 576 oC to 620 oC at 250 g/Nm after post-deposition annealing at 350 oC in a forming gas ambient. Instead of using a p-type amorphous silicon layer, high work function MoOx films as hole selective contact are applied for heterojunction silicon solar cells and the best efficiency yet recorded (21 %) is obtained.