Bigger but fewer pellets. An ounce of 00 (2/0) buckshot won't penetrate as much as an ounce of 0000 (4/0) buckshot, but there'll be less hits on the target.
I notice 000 in 20 gauge is damn good early game as you can take out stuff like Radscorpions with it, which tended to need slugs before (which aren't sold much).
Sergeant RL-3,
12 gauge is pretty close to 20mm in diameter (18.5mm actually).