UV absorption of RbAg4I5-RE (Sm, Yb) thin-film systems

UV spectra of samples prepared by vacuum deposition of Sm and Yb thin films on 100–200-nm thick films of the RbAg₄I₅ solid electrolyte (SE) at 300–350 K contain strong absorption bands peaking at about 4.3 and 5.0 eV. After deposition of ～5 nm of Sm, the ionic conductivity σ of the samples decreases from σ ₀ to ≈0.9 σ ₀, and the SE lattice parameter, from 11.24 to ≈11.15 Å, with the x-ray reflection halfwidth increasing from 0.5 to 0.8°. Further growth of Sm concentration in the samples changes the x-ray diffraction pattern, the absorption at 4.3 and 5.0 eV increases, a new absorption edge forms at 3.8 eV, and σ decreases down to ～10^?2 σ ₀. It is conjectured that the strong UV absorption bands in heavily defected silver halides of the RbAg₄I₅-Sm(Yb) system is genetically related to the 4d ¹⁰→4d ⁹5s electronic transitions in free Ag⁺ ions.