The advantages and limitations of photovoltaic solar modules for energy generation are reviewed with their operation principles and physical efficiency limits. Although the main materials currently used or investigated and the associated fabrication technologies are individually described, emphasis is on silicon-based solar cells. Wafer-based crystalline silicon solar modules dominate in terms of production, but amorphous silicon solar cells have the potential to undercut costs owing, for example, to the roll-to-roll production possibilities for modules. Recent developments suggest that thin-film crystalline silicon (especially microcrystalline silicon) is becoming a prime candidate for future photovoltaics.