This is one of my favorite features of RDS: You can set a maintenance window and have the option to not have changes take effect until that window. So if I want to upgrade Postgres or change the instance size, I set it up and the downtime happens when I'm fast asleep and nobody is using the site.
I also think (but not 100% sure) that if you have Multi-AZ enabled, changes are done by upgrading the slave, failing over, and then upgrading the ex-master, so downtime is limited to the failover period.