Generally, in a spin or in any other stalled condition, aileron has the opposite effect if any. A stall is cause by going past the critical angle of attack. If you are stalled and apply aileron to counteract, the aileron increases the angle of attack, and therefore has the opposite effect. Rudder in the opposite direction of the spin will yaw the plane in the opposite direction, therefore increasing the speed of that wing, and hopefuly unstalling it.