PHP cant do this.... it can create folders (ie mailboxes) but not an account (blah@something.com where the account it blah). To do this you need to either create a real account on the machine, or wig out the mail server into someone setting up virtual accounts. None of which involve PHP. There are a couple of ways I can think of under *nix systems to setup virtual accounts, but I dont know about windows.
Hope this Helps some 🙂 !