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The Ultimate Horn in Leafgreen is not an item, it's a pokemon. Heracross. You can find him on island 6 in the paddock on left from the horn house.
In Pokemon Crystal Version, a Heracross will occasionally appear when you use headbutt on trees.
on route 6665
Piplup does not exist in Pokemon LeafGreen or FireRed.
Heracross is the Bug horned Pokemon. It can only be found in honey trees but still they are very rare. Sincerely Chicken Lord