Insertion of 3d- and 4f-Elements into Silver Iodide

The interaction of manganese and some 4f-metals (M) with silver iodide is studied. The samples are obtained by sputtering M onto the surface of polycrystalline AgI films (0.2 m, 300 K) in a vacuum. Optical absorption in the samples is interpreted as the insertion of M ions into AgI with the formation of dopants AgI:M. A new phase with an optical bandgap of 3.7 eV emerges in the samples with elevated concentrations of La, Ce, Pr, Nd, Sm, or Dy (n _M/n _Ag 0.1). X-ray diffraction patterns for such samples with Sm correspond to structures with large interfacial distances, for example, 0.99, 0.87, 0.76, and 0.67 nm. In air, AgI forms in the samples with a new phase; this process is hindered by the sputtered protective coatings. According to optical absorption data, X-ray diffraction, and local microanalysis the Mn insertion into AgI is followed by the formation of a new phase (2Ag:Mn:4I), which may belong with solid electrolytes Ag₂MI₄, where nonmagnetic M are known (Zn, Cd, Sn, Hg, Pb).