LAUSR

Bismuth telluride‐based thermoelectric (TE) materials are historically recognized as the best p‐type (ZT = 1.8) TE materials at room temperature. However, the poor performance of n‐type (ZT≈1.0) counterparts seriously reduces the efficiency of the device. Such performance imbalance severely impedes its TE applications either in electrical generation or refrigeration. Here, a strategy to boost n‐type Bi2Te2.7Se0.3 crystals up to ZT = 1.42 near room temperature by a two‐stage process is reported, that is, step 1: stabilizing Seebeck coefficient by CuI doping; step 2: boosting power factor (PF) by synergistically optimizing phonon and carrier transport via thermal‐driven Cu intercalation in the van der Waals (vdW) gaps. Theoretical ab initio calculations disclose that these intercalated Cu atoms act as modulation doping and contribute conduction electrons of wavefunction spatially separated from the Cu atoms themselves, which simultaneously lead to large carrier concentration and high mobility. As a result, an ultra‐high PF ≈63.5 µW cm−1 K−2 at 300 K and a highest average ZT = 1.36 at 300–450 K are realized, which outperform all n‐type bismuth telluride materials ever reported. The work offers a new approach to improving n‐type layered TE materials.