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Line 12 muffin cups with cupcake liners. Set aside.
In a small microwave-safe bowl, place half of the chocolate. Melt the chocolate by heating in 30-second increments and stirring in between. This should take 30 to 60 seconds total. The chocolate should be smooth.
Scoop about 1/2 tablespoon of melted chocolate into each cupcake liner. This can be done by scooping the chocolate with one spoon and scraping it off with another.
Shake the pan periodically back and forth to help spread the chocolate so that it covers the bottom of the liner.
Freeze for 15 minutes.
While the chocolate is freezing, prepare the peanut butter filling. Measure peanut butter, powdered sugar, and butter into a medium mixing bowl. Using a hand mixer, mix until creamy.
Put 1 tablespoon of the peanut butter filling on top of the chocolate layer, making sure the filling does not touch the sides of the cupcake liner.
Freeze for 5 minutes.
In a microwave-safe bowl (use the one from Step 2), melt the remaining chocolate in the same way as explained in Step 2.
Cover the peanut butter layer with the melted chocolate.
Freeze for 10 to 15 minutes or refrigerate for 15 to 20 minutes until hardened.