The Home button is a very dangerous button to override and, because of that, Android will not let you override its behavior the same way you do the BACK button.
Take a look at this discussion.
You will notice that the home button seems to be implemented as a intent invocation, so you’ll end up having to add an intent category to your activity. Then, any time the user hits home, your app will show up as an option. You should consider what it is you are looking to accomplish with the home button. If its not to replace the default home screen of the device, I would be wary of overloading the HOME button, but it is possible (per discussion in above thread.)