I would not really call it a buzz word, if you include the HTML 5 doctype then you're using HTML 5 - simple as.
Also I'd recommend you stick with Python, PHP is quite a terrible language when you get to know it better.
HTML5 is just a buzz word for a set of standards, if you know HTML there's no need to "learn" HTML5. You'll also want to look into CSS and Javascript once you're done.
I learnt through setting projects for myself, Googling problems, asking people questions, looking at W3Schools and Tizag.
Off topic but useful, the great thing about dynamic languages such as PHP though is that once you know one, you pretty much know them all. I learnt Python at Uni and I just found I can actually code PHP once I've looked the syntax up for 5 minutes.
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