One heats water – which is not too hard to understand – you know if you leave something out in the sun for long enough it will get warmer and water has a high heat capacity – it can store a lot of heat energy.
Photovoltaic cells – those that use sunlight to make electricity, are quite different. They contain special materials with special properties – known as semiconductors. Light energy from the sun is absorbed by these semiconductors, knocking electrons lose, which causes a flow of electricity!
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