Here, we present a study of thermoelectric devices with amorphous silicon/zinc oxide (a-Si/ZnO)stacked hetero-structures fabricated using both radio frequency magnetron sputtering and rapid thermal annealing techniques. Overall, the Seebeck coefficient (S) and power factor (S-2 sigma, where sigma is the electrical conductivity) of the a-Si/ZnO-stacked hetero-structures were found to be superior to those of pure a-Si structures. In particular, the Seebeck coefficient and power factor of the a-Si/ ZnO (9/8 layers)-stacked hetero-structures were about 1.6 and 23.8 times those of the pure a-Si structures, respectively. These improvements can be attributed to hole blocking by the a-Si/ZnO potential barriers formed at the interface between the ZnO layer with a wide energy bandgap and the a-Si layer with a relatively narrow bandgap. In addition, the a-Si and ZnO materials used in this work are non-toxic, earth-abundant, and cheap, and the fabrication processes were simple and costeffective, making the hetero-structures suitable for use in non-toxic and biocompatible thermoelectric devices and also for micro-energy harvesting applications. Published by AIP Publishing.