I think the PhD is the only one that either you do it now or never. So, if you’re interested, I’d go for that.
Google will send you email offers for the rest of your life, so I’d keep it last in my list. You can also replace Google with many other co.
Startup I don’t recommend starting one unless you have a problem to solve and money. PhD can help you work on some good tech, but don’t forget about a good problem. Google can help you with money, but again you have many other options.