Stability and electronic properties of CsK$_2$Sb surface facets

Abstract

First-principles methods have recently established themselves in the field of photocathode research to provide microscopic, quantum-mechanical characterization of relevant materials for electron sources. While most of the existing studies are focused on bulk crystals, the knowledge of surface properties is essential to assess the photoemission performance of the samples. In the framework of density-functional theory, we investigate stability and electronic properties of surface slabs of CsK$_2$Sb, an emerging semiconducting photocathode material for particle accelerators. Considering surfaces with Miller indices 0 and 1, and accounting for all possible terminations, we find that, at the interface with vacuum, the atomic layers may rearrange considerably to minimize the electrostatic repulsion between neighboring alkali species. From the analysis of the surface energy as a function of the chemical potential, we find a striking preference for surfaces oriented along the (111) direction. Yet, at large and intermediate concentrations of Cs and K, respectively, (100) and (110) slabs are energetically most favorable. The considered surfaces exhibit either semiconducting or metallic character. Of the former kind is the most stable (111) slab which has a band gap of about 1.3 eV, in excellent agreement with experimental values for CsK$_2$Sb samples. Metallic surfaces have lower work function, on the order of 2.5 eV, in line with the emission threshold measured for CsK$_2$Sb photocathodes. All in all these results contribute to the fundamental understanding of the microscopic properties of CsK$_2$Sb in particular and of multi-alkali antimonides in general, and represent an useful complement to the ongoing experimental efforts in the characterization of this emerging class of photocathode materials.