High-throughput roll-to-roll processing could be used to scale up the manufacture of flexible thermoelectric generators. Very thin thermoelectric layers can be manufactured at high throughput speed and low cost and, most importantly, are predicted to possess better thermoelectric properties than thicker layers. Here we present a study on a series of bismuth telluride films of different thickness (few nm to 370 nm), deposited on polymer substrates at room temperature using DC magnetron sputtering. Unlike previous studies of deposition of bismuth telluride films onto heated substrates, an island-growth mode, indicated by AFM, was observed for Bi-Te films grown at room temperature. A period of growth in which the layer only partially coats the substrate, with only imperfect connections between islands, was observed. In this partially coated region, the coating exhibited an extremely high Seebeck coefficient. An energy barrier mechanism, similar to the interface effect in nanomaterials, is proposed to explain this phenomenon, along with a possible quantum confinement effect. We found that a thinner Bi-Te film could generate a greater power factor because of a quasidecoupling of Seebeck coefficient and electrical resistivity. In addition, ensuring that the