A thermopile is simply an array of thermocouples connected in series and close together. The most common application is when a voltage is applied to cool one side of the thermopile and whatever it is bonded to.
Thermopiles for laser power measurement, however, are used in the opposite fashion. That is, a temperature difference is used to create a voltage. On one side, the material heated by a laser (or any other radiation source), and on the other side is a heatsink. The laser's energy that is absorbed by the material is converted to heat.