β-Phase Yb 5 Sb 3 H x : Magnetic and Thermoelectric Properties Traversing from an Electride to a Semiconductor.

An electride is a compound that contains a localized electron in an empty crystallographic site. This class of materials has a wide range of applications, including superconductivity, batteries, photonics, and catalysis. Both polymorphs of Yb 5 Sb 3 (the orthorhombic Ca 5 Sb 3 F structure type (β phase) and hexagonal Mn 5 Si 3 structure type (α phase)) are known to be electrides with electrons localized in 0D tetrahedral cavities and 1D octahedral chains, respectively. In the case of the orthorhombic β phase, an interstitial H can occupy the 0D tetrahedral cavity, accepting the anionic electron that would otherwise occupy the site, providing the formula of Yb 5 Sb 3 H x . DFT computations show that the hexagonal structure is energetically favored without hydrogen and that the orthorhombic structure is more stable with hydrogen. Polycrystalline samples of orthorhombic β phase Yb 5 Sb 3 H x ( x = 0.25, 0.50, 0.75, 1.0) were synthesized, and both PXRD lattice parameters and 1 H MAS NMR were used to characterize H composition. Magnetic and electronic transport properties were measured to characterize the transition from the electride (semimetal) to the semiconductor. Magnetic susceptibility measurements indicate a magnetic moment that can be interpreted as resulting from either the localized antiferromagnetically coupled electride or the presence of a small amount of Yb 3+ . At lower H content ( x = 0.25, 0.50), a low charge carrier mobility consistent with localized electride states is observed. In contrast, at higher H content ( x = 0.75, 1.0), a high charge carrier mobility is consistent with free electrons in a semiconductor. All compositions show low thermal conductivity, suggesting a potentially promising thermoelectric material if charge carrier concentration can be fine-tuned. This work provides an understanding of the structure and electronic properties of the electride and semiconductor, Yb 5 Sb 3 H x , and opens the door to the interstitial design of electrides to tune thermoelectric properties.