Lightly coat 4 (2-ounce) ramekins with cooking spray, and sprinkle 3/4 teaspoon sugar into each of the ramekins, shaking and turning to coat. Set prepared ramekins aside.
Combine 1/2 cup plus 2 tablespoons sugar, milk, and cocoa in a small saucepan, stirring well with a whisk. Bring to a boil over medium heat. Cook 30 seconds or until sugar dissolves, stirring constantly. Remove from heat; add the butter and 1/2 ounce unsweetened chocolate. Stir until the chocolate melts and mixture is smooth. Cool chocolate mixture 10 minutes.
Add flour, vanilla, salt, and egg white to chocolate mixture, stirring with a whisk just until blended. Spoon 2 tablespoons chocolate mixture into each prepared ramekin, and top each with 2 teaspoons chocolate chips. Divide the remaining chocolate mixture evenly among ramekins, spreading to cover the chocolate chips. Bake at 350° for 20 minutes or until barely set. Cool for 10 minutes. Invert onto dessert plates. Serve warm.