An ultra-thin LiF layer in conjunction with an Al layer is employed as the electron collector for the a-Si:H based single-junction thin film photovoltaic cell. The cell has the structure of boron doped μ-SiO_x (hole collector) - intrinsic a-Si:H (photoactive layer) - LiF / Al (electron collector and back electrode). The substrate used is U type Asahi glass, which is also acting as the transparent front electrode. For the cell with the 1.5 nm thick LiF layer, annealed at 120^°C, the open current voltage (V_OC) of 0.936 V, the short current density (J_SC) of 13.598 mA/cm², and the fill factor (FF) of 0.690 are achieved. The J_SC and V_OC values are comparable to the values measured for the a-Si:H based p-i-n reference cell, but the FF value is found to be lower, which is attributed to the losses due to recombination at the intrinsic a-Si:H / LiF / Al junction. The current versus voltage measurements are carried out under the standard test conditions. The J_SC values are corrected according to the external quantum efficiency measurements of the cells in the AM1.5 spectrum region between 270 nm and 800 nm.