The picture of himself Lucifer sets as Chloe's desktop wallpaper is a part of a photo shoot Tom Ellis did for "Attitude" magazine in 2012.
You can see the plant Lucifer helpfully "watered" with booze in the upper right corner of Chloe's reorganized desk, neatly placed and very thoroughly dead.
The title is spoken by Lucifer.
When Lucifer reveals that Marcus is Cain, he says, "Or would you prefer 'Mr. Cain?'" Dean Cain played Clark Kent/Superman on Lois & Clark: The New Adventures of Superman (1993) prior to Tom Welling's portrayal on Smallville (2001).