Optical and electrical characteristics of n-type nano-crystalline-silicon oxide (n-µc-SiO:H) materials can be varied to optimize and improve the performance of a solar cell. In silicon heretojunction (SHJ) solar cells, it can be used to improve carrier selectivity and optical transmission at the front side, both of which are vitally important in device operation. For this purpose, the n-µc-SiO:H was investigated as the front surface field (FSF) layer. During film deposition, an increased CO2 flow rate from 0 to 6 sccm resulted in changes of crystalline volume fractions from 57 to 28%, optical band-gaps from 1.98 to 2.21 eV, dark conductivities from 7.29 to 1.1 × 10−5 S/cm, and activation energies from 0.019 to 0.29 eV, respectively. In device applications, a minimum optical reflection was estimated for the FSF layer that was fabricated with 4 sccm CO2 (FSF-4), and therefore obtained the highest external quantum efficiency, although short circuit current density (Jsc) was 38.83 mA/cm2 and power conversion efficiency (PCE) was 21.64%. However, the highest PCE of 22.34% with Jsc = 38.71 mA/cm2 was observed with the FSF prepared with 2 sccm CO2 (FSF-2), as the combined opto-electronic properties of FSF-2 were better than those of the FSF-4.