Super low work function of alkali-metal-adsorbed transition metal dichalcogenides.

Discovering the materials that have work functions less than 1 eV is essential for efficient thermionic energy converter (TEC). The lowest work function of materials reported so far is in a range of about 1 eV. Here, to design low work function materials, we perform first-principles calculations on selected materials of transition metal dichalcogenide as substrates and alkali metals as adsorbates. The work function of our selected materials has a dip ubiquitously independent of the true binding distances of the adsorbates and exhibits contrasting behavior between empty d-shell elements (K, Rb, and Cs) and the others (Li and Na). We show that the interaction of empty d-orbitals of alkali metals and lone pair electrons of chalcogen is a key to the behavior of the work function. From calculated key parameters that determine the work function, we find that, regardless of the amount of charge transfer, K on WTe2 induces the largest surface dipole moment, which consequently makes the surface work function of as small as 0.8 eV, the smallest reported to date, and that the work function is lowered further to 0.7 eV by lattice strains. We demonstrate that the thermal efficiency of TEC using the low work function material exceeds that of thermoelectric materials with figure of merit of 5-10 in temperature range of 880-1200 K.