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It looks like I may have been a little off on the explanation. Specifically attributing the movement of charge carriers exclusively to the electric field that build up. Read more about that here:

https://www.quora.com/How-do-solar-ce...

Animations by Dom Burgess. His brilliant channel, Every Think, is here:

   / @domburgess  

Part 1 demonstration video is here:    • Why all solar panels are secretly LED...  

Photovoltaic cells and LEDs are both made of diodes. Diodes are designed to allow electricity to flow in one direction only but the way we make them (out of semiconductors) means that can absorb and emit light.

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