Preheat oven to 350°F. Spray the muffin pan with nonstick cooking spray or just rub the insides with cooking oil.
To make the cakes, combine the cake mix, combine cake mix, sour cream, egg, coffee granules and water. The batter should be thick.
If using regular sized muffin pans: divide batter evenly among cups of pan. Bake 10-12 minutes or until wooden pick inserted in centers comes out clean.
If using Pampered Chef Deluxe Mini Muffin Pan: spoon 1 tablespoon of filling in each cup. Bake 8-10 minutes or until wooden pick inserted in centers comes out clean. Repeat with remaining batter.
Meanwhile, mix together the mascarpone cheese, just 1/4 cup of powdered sugar, vanilla extract. Put in plastic bag for piping and set aside. You can also place your whipped topping in a plastic bag for piping and refrigerate until needed. Place remaining 2 tablespoons of the powered sugar in a small bowl and have your tart-shaper (or whatever you will use to create the indentations) ready.
When the cakes are done, immediately make the indentations with the tart-shaper. Dip the tart-shaper in the powdered sugar to prevent the cake from sticking to tart-shaper. Brush the tops of each cake with the coffee liqueur. Move the cakes to a cooling rack to cool completely.
Trim corners of both bags. Pipe filling over cakes. Pipe whipped topping over filling. Sprinkle with shaved chocolate or cocoa powder.