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1 2006

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Structural phase transitions and their influence on Cu+ mobility in superionic ferroelastic Cu6PS5I single crystals

Gągor A., Pietraszko A., Drozd M., Połomska M., Kaynts D.

Materials Science Poland

2006

Vol. 24, No. 1

237--243

The structural origin of Cu+ ion conductivity in Cu6PS5I single crystals is described in terms of structural phase transitions studied by X-ray diffraction, polarized light microscopy and calorimetric measurements. Below the phase transition temperature at Tc = (144-169) K, Cu6PS5I belongs to the monoclinic, ferroelastic phase, with the space group Cc. Above Tc, the crystal changes its symmetry to a cubic superstructure, with the space group F43c (a' = 19.528); finally, at 274 K, the disordering of Cu+ ions increases to the symmetry F43m (a = 9.794). The phase transition at 274 K coincides well with a strong anomaly in electrical conductivity observed on the Arrhenius plot. Diffusion paths for Cu+ ions are evidenced by means of atomic displacement factors and a split model. The influence of copper stoichiometry on Tc is also discu