Are you trying to work with hexadecimal numbers or with characters? Decrementing operators are not supposed to work on characters.
If with characters, you would need to do the following - take a look at chr() and ord() functions. chr() will return the character according to the ascii code, ord - return ASCII code for character.
Therefore, to get the "E" from "F" you will need the following:
$a="F";
$b=ord($a);
$a=chr(--$b);