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Get a graphics tablet if you want to draw or sculpt digitally. I use Wacam's Bamboo Tablet.
If you can't or don't want to draw characters over and over or at all but want to have 2D images of them, you can render them from 3D models
You can also rotoscope them to get a more 2D look (if the results from 3D and filters aren't to your liking) (video example from OtaKing77077)
PaintTool Sai is a 2D software with less clutter than Photoshop and, faster to load and work in.
Blender is a free program that allows you to do many different things, including (but not limited to) 3D modelling/sculpting/texturing/rendering/animation/physics, 2D drawing/animation, audio/video compositing
While Blender and Scultptris are free programs that you can sculpt in, Zbrush allows to you sculpt with greater detail and more tools dedicated to sculpting
Makehuman offers free 3D character creation that you can use for pretty much whatever you want.
Daz3D offers more appealing characters but generally cost money and are more difficult to work with in other programs.