Let’s start with how fluorescence works, before we jump into the photoelectric effect. When you shine light on an object, the photons can interact with the electrons in the atoms on the outside of the object. In a fluorescent effect, the photons bump the electrons into a higher energy state absorbing the photon’s energy and destroying it. Electrons don’t like that, and they pop back where they belong. Sometimes the pop back warms the object, but with a fluorescent object the pop back creates a photon, the specific color of the fluorescence you see.
Now that you can see how light in leads to higher energy electron leads to light out, you can ask “What about if I put in more energy?”. Special materials aren’t as tough as fluorescent paint molecules, and when light hits them it bumps the electron so hard it comes off. Now you’ve got a loose electron wandering around, trying to find the atom it came off of. As soon as it does, everything is back to normal.
Now you engineer a very thin slab of this material and put a transparent electrode on the top of it. Now when the electron pops off, it is conducted away. It is forced to go through a circuit before it can get back to the thin slab of material and find its way back to where it goes. This is how a solar cell works. Light bumps a bunch of electrons loose, they are forced to go through a circuit (where they do some useful work) before they can get back home again.
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