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 Yb₅Sb₃ (the orthorhombic Ca₅Sb₃F structure type (β phase) and hexagonal Mn₅Si₃ 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 Yb₅Sb₃H_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 Yb₅Sb₃H_x (x = 0.25, 0.50, 0.75, 1.0) were synthesized, and both PXRD lattice parameters and 1H 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 Yb³⁺. 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, Yb₅Sb₃H_x, and opens the door to the interstitial design of electrides to tune thermoelectric properties.

After sintering, the pellets, Yb₅Sb₃H_x, were polished with sandpaper and isopropanol to remove any surface oxide and transferred into a glovebox to be ground in an agate mortar and pestle and sieved for PXRD. The samples were removed from the glovebox and loaded onto a zero background X-ray plate via solvent smear (ethanol) for data collection in a Bruker D8 Eco Advance diffractometer with Cu Kα radiation operating at 40 kV and 25 mA. Diffraction data were collected from 2θ range 15−70° with a 0.015 step size and 1 s scan rate per step. Rietveld refinement employing the crystallographic information file (CIF) for β-Yb₅Sb₃ was carried out using Topas5 software to refine lattice parameters and determine the phase purity of the samples. H position or occupancy was not refined.