The opportunities for photovoltaic (PV) solar energy conversion are reviewed in the context of projected world energy demands for the twenty-first century. Conventional single-crystal silicon solar cells are facing increasingly strong competition from thin-film solar cells based primarily on polycrystalline absorber materials, such as cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS). However, if PVs are to make a significant contribution to satisfy global energy requirements, issues of sustainability and cost will need to be addressed with increased urgency. There is a clear need to expand the range of materials and processes that is available for thin-film solar cell manufacture, placing particular emphasis on low-energy processing and sustainable non-toxic raw materials. The potential of new materials is exemplified by copper zinc tin sulphide, which is emerging as a viable alternative to the more toxic CdTe and the more expensive CIGS absorber materials.