The crystallization of hydrogenated amorphous silicon (a-Si:H) is essential for improving solar cell efficiency. In this study, we analyzed the crystallization of a-Si:H via excimer laser annealing (ELA) and compared this process with conventional thermal annealing. ELA prevents thermal damage to the substrate while maintaining the melting point temperature. Here, we used xenon monochloride (XeCl), krypton fluoride (KrF), and deep ultra-violet (UV) lasers with wavelengths of 308, 248, and 266 nm, respectively. Laser energy densities and shot counts were varied during ELA for a-Si:H films between 20 and 80 nm thick. All the samples were subjected to forming gas annealing to eliminate the dangling bonds in the film. The ELA samples were compared with samples subjected to thermal annealing performed at 850–950 °C for a-Si:H films of the same thickness. The crystallinity obtained via deep UV laser annealing was similar to that obtained using conventional thermal annealing. The optimal passivation property was achieved when crystallizing a 20 nm thick a-Si:H layer using the XeCl excimer laser at an energy density of 430 mJ/cm2. Thus, deep UV laser annealing exhibits potential for the crystallization of a-Si:H films for TOPCon cell fabrication, as compared to conventional thermal annealing.