Hot-Injection Synthesis of Cu-Doped Cu₂ZnSnSe₄ Nanocrystals to Reach Thermoelectric zT of 0.70 at 450°C.

As a new class of potential midrange temperature thermoelectric materials, quaternary chalcogenides like Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) suffer from low electrical conductivity due to insufficient doping. In this work, Cu-doped CZTSe nanocrystals consisting of polygon-like nanoparticles are synthesized with sufficient Cu doping contents. The hot-injection synthetic method, rather than the traditional one-pot method, in combination with the hot-pressing method is employed to produce the CZTSe nanocrystals. In Cu-doped CZTSe nanocrystals, the electrical conductivity is enhanced by substitution of Zn(2+) with Cu(+), which introduces additional holes as charge carriers. Meanwhile, the existence of boundaries between nanoparticles in as-synthesized CZTSe nanocrystals collectively results in intensive phonon-boundary scatterings, which remarkably reduce the lattice thermal conductivity. As a result, an average thermoelectric figure of merit of 0.70 is obtained at 450 °C, which is significantly larger than that of the state-of-the-art quaternary chalcogenides thermoelectric materials. The theoretical calculations from the Boltzmann transport equations and the modified effective medium approximation are in good agreement with the experimental data.