I just wanted to start learning programming on the AVR microcontroller, but when you request samples it seems like that is for big companies. I am just a student/hobbyist so is it OK to order samples from them?
well its intended for companies that are trying to decide which device(s) they want to use for their product. The idea is that giving them free samples they'll come back with large orders (thousands). A few people I know request samples from companies for all sorts of things (many they have no use for). It doesn't hurt to ask. I wouldn't lie though, its just unethical. If they give you the sample => cool. Else you didn't loose anything.