Your quality as a programmer is more important than the language you find yourself most comfortable in (I'm very comfortable with QuickBasic, but employers are more interested in the fact that I'm creative, curious, motivated, love programming, and know a heck of a lot about computers).
If you find you enjoy PHP programming more than Java programming, that means you will probably be more productive in a PHP-related job.
If you think mastering Java will substantially expand your programming abilities as a whole (rather than just the number of languages you are versed in) then it's probably a good idea.
Java and PHP are different, but not that different. I would suggest you get some experience further away from the familiar. Perhaps do some embedded programming in C, or learn Haskell. Even if you find that they're not your cup of tea, you'll learn a heap of stuff quickly.