To melt the chocolate you can do this in the microwave by placing the chocolate in a microwave-safe bowl and cooking 30 seconds mixing and then repeat microwaving in 30-second intervals stirring until smooth and completely melted. Or you can make temperated chocolate by using the double boiler method.
Place cupcake liners into a muffin pan and then brush a layer of chocolate onto the liners to cover.
Refrigerate the chocolate cups until firm, about 30 minutes.
Once completely solid remove the cups from the liners and use as desired.
Notes
Make sure you're making a thick layer of chocolate, if it's too thin it will break when you remove it from the liners.
You can refrigerate them, but keep in mind chocolate can absorb flavors, it's best to keep them in a container if possible.
If you'll be serving outside try to keep them in a shaded area as it's chocolate and they can melt.