Solid State Ionics, Vol.154, 265-271, 2002
I-129-Mossbauer spectroscopy study of MI-As2Se3 (M-Ag, Cu) superionic chalcohalide glasses
I-129-Mossbauer spectroscopy was used to study the local iodine environment in the superionic xAgI.(l-x)As2Se3 and mixed conducting (Cu+, hole) xCuI.(I-x)As2Se3 glassy systems (x=0.05-0.50). Well-resolved quadrupole-split multiplets, also characterised by a Gaussian-like distribution of the nuclear quadrupole interaction constant v(Q), as well as distinctly different values of the isomer shift S compared to that of c-AgI and c-CuI (0.3 less than or equal to DeltaS less than or equal to 0.6 mm s(-1)), clearly indicate fundamental differences of the iodine local environment in the MI-As2Se3 glasses and crystalline superionic alpha-phases of these metal iodides. Hyperfine interaction parameters of both the glassy systems as a function of x exhibit, however, different trends for the AgI- and CuI-containing glasses. In contrast, the two systems show a remarkable common decrease of the absorber recoil-free fraction f(A) by a factor of 3-5 and, respectively, of the local Debye temperature Theta(D) with increasing x. These and other spectroscopic features are consistent with the recent high-resolution neutron diffraction results and two drastically different ion transport regimes at low and high mobile ion content and will be discussed in the present contribution.
Keywords:iodine local environment;superionic chalcohalide glasses;I-129-Mossbauer spectroscopy;metal iodide molecular dispersion and;clustering