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This was made in Adobe Photoshop 8.0. and includes selective coloring.
1. Duplicate your base and set it to SCREEN until it's as light as you desire.
2. Go to Layer >> New Fill Layer >> Solid Color and choose a dark gray (I used #959595). Set this layer to COLOR BURN. Play around with the grays until you get it to your desired level of darkness.
3. Now I want to add a little bit of yellow to Dean's face, so make a new solid color layer and choose a light yellow (I used #F3EADC). Then set that layer to MULTIPLY at whatever opacity looks best to you.
4. I also want to add some pink. (CAN YOU GUESS HOW???) Make another new solid color layer and choose a lovely light pink (#F897B2). Set that to SOFT LIGHT.
5. Once again I want more yellow, but I also want some more darkness to it. I used the same yellow I had before, so duplicate that one and set it to COLOR BURN to add both color and darkness.
6. Now I did some Selective Coloring. In the REDS, I pushed the CYAN way into the negative numbers to add lots of red. To counteract the fact that now Dean looked like he had an angry rash, I moved the MAGENTA to about -30 to get rid of some of that color. I took away some yellow by moving the YELLOW back a little as well. As for the BLACK, I moved that up to about 20 for even more darkness.
I also went to the WHITES and moved the YELLOW back to about -15.
7. Next, go to Layer >> New Adjustment Layer >> Brightness/Contrast. I moved up the Contrast to about 17 just for that sharp look.
8. Lastly, I made THIS NIFTY THING!
It's so easy to make. Just make a solid black layer, then choose a large rounded brush and click right in the middle to make that white circle. I love this effect! Then just set it to SOFT LIGHT at whatever opacity looks good to you for that nice pretty highlight.
And you're done!
To sharpen I usually go all the way to the bottom of my layer pallete, duplicate my base, go to Filter >> Sharpen >> Sharpen, and set that to around 40%, or whatever looks sharp enough. I always sharpen at the end, because you keep duplicating sharpened layers, your icon will come out looking more and more jagged.
Enjoy!