Interface-Enhanced High-Temperature Thermoelectricity in Cu_1.99Se/B₄C Composites with Synergistically Improved Mechanical Strength

Degenerate semiconductors usually demonstrate a metallic-like conduction behavior, showing limited carrier mobility at high temperatures. Herein, by incorporating B4C nanoparticles into the Cu1.99Se system, an unusual switch from the "degenerate" to "non-degenerate" semiconducting behavior is revealed as a result of the engineered interfaces. Heterogeneous interfaces and disordered Cu2Se amorphous phases are introduced in the Cu1.99Se/B4C composites, which generate a trapping effect against the mobile Cu ions, leading to a distinctive "hump" signature for electrical conductivity. Benefiting from this rare high-temperature thermoelectric response, a high power factor is obtained due to reduced carrier concentration and enhanced mobility, and low lattice thermal conductivity is retained because of relatively stronger anharmonic lattice vibrations. Consequently, the Cu1.99Se + 0.9 vol.% B4C sample at least achieves a maximum thermoelectric figure of merit (ZT) of 2.6 at 1025 K with synergistically enhanced mechanical robustness. The present interface engineering strategy may be applicable to other thermoelectric materials with ionic migration characteristics.