Photoshop's cool, but if you wanna trace the characters or a scene you have to go with a vector based program (photoshop's a raster-based program which means it's pixellated).
So I'd go with Illustrator without hesitation.
Photoshop does have the pen tool, so you can do some vector work but illustrator revolves around that and, though it's a little tougher to learn, it's so much cleaner. here's one site that explains the differences between raster and vector:
http://www.nw-media.com/ps_intro/html/lesson_1/lesson1_pg3.html