Use File.ReadAllBytesto read bytes of a file as a byte array.
byte[] bytes = File.ReadAllBytes('file.exe');
If you want to convert this to a hexadecimal string (and I would not advise doing it at all - the strings are immutable in C #, so to modify even one byte you will need to copy the rest of the string), for example, use:
string hex = BitConverter.ToString(bytes);