Regardless of how Java actually stores the char datatype, what's certain is this, the character 'A' subtracted from the character 'A' would be represented as the null character, \0. In memory, this means every bit is 0. The size in memory a char takes up in memory may vary from language to language, but as far as I know, the null character is the same in all the languages, every bit is equal to 0.
As an int value, a piece of memory with every bit equal to 0 represents the integer value of 0.
And as it turns out, when you do "character math", subtracting any alphabetical character from any other alphabetical character (of the same case) results in bits being flipped in such a way that, if you were to interpret them as an int, would represent the distance between these characters. Additionally, subtracting the char '0' from any other numeric char will result in int value of the char you subtracted from, for basically the same reason.
'A' - 'A' = '\0'
'a' - 'a' = '\0'
'0' - '0' = '\0'
