Gallium-doped zinc oxide (GZO) thin films were deposited on glass, and the process parameters are RF power of 50 W and working pressure of 5 mTorr, and the substrate temperature was changed from room temperature to 300°C. At first, the thickness was around 300 nm by controlling the deposition time. The effects of substrate temperature on the crystallinity, lattice constant (c), carrier mobility, carrier concentration, resistivity, and optical transmission rate of the GZO thin films were studied. The 200°C-deposited GZO thin films had the best crystallinity, the larger carrier concentration and carrier mobility, and the lowest resistivity. For that, the thickness of the GZO thin films was extended to around 1000 nm. Hydrochloric (HCl) acid solutions with different concentrations (0.1%, 0.2%, and 0.5%) were used to etch the surfaces of the GZO thin films, which were then used as the substrate electrodes to fabricate the p-i-n α-Si:H thin-film solar cells. The haze ratio of the GZO thin films increased with increasing HCl concentration, and that would effectively enhance light trapping inside the absorber material of solar cells and then improve the efficiency of the fabricated thin-film solar cells.