"Sorcerers learn a number of cantrips, or 0-level spells, as noted on Table: Sorcerer Spells Known under “Spells Known.” These spells are cast like any other spell, but they do not consume any slots and may be used again."
Before shouting, "The at-will ability only applies to spells known according to that table!" consider the feat
Extra Cantrips or Orisons from
Ultimate Magic, which, each time is taken, grants the owner two additional level 0 spells (cantrips or orisons) beyond the limits listed on that chart. Additionally, the cantrips or orisons known need not be from the same class, nor from a class in which you have levels. Additionally, the feat
Expanded Arcana, each time you take it, allows learning an additional spell (or two) from your class list. Thus, in both cases, there is precedent in Pathfinder alone for a spontaneous caster expanding his spells known beyond the chart, and in the first case, casting level 0 spells (at will) from outside his class's spell list.