In a microwave, melt chocolate chips and shortening; stir until smooth. Using a narrow pastry brush, brush the inside of eighteen 2-in. foil muffin cup liners with 1/2 teaspoon melted chocolate. Refrigerate for 15 minutes or until firm. Repeat layers twice. Chill until set.
In a large heavy skillet, cook sugar over medium-low heat until melted and a golden amber color. Gradually stir in cream; cook and stir until sugar is dissolved. Add liqueur and espresso powder; stir until smooth. Stir in white chocolate until melted. Transfer to a small bowl; cover and refrigerate for 1-2 hours or until slightly thickened.
Carefully remove and discard foil liners from chocolate cups. Spoon or pipe filling into cups; garnish with coffee beans. Store in an airtight container in the refrigerator.