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

The structural origin of Cu+ ions conductivity in Cu6PS5I single crystals is described in terms of structural phase transitions studied by X-ray diffraction, polarizing microscope and calorimetric measurements. Below the phase transition at Tc=(144-169) K Cu6PS5I belongs to monoclinic, ferroelastic phase, space group Cc. Above Tc crystal changes the symmetry to cubic superstructure, space group F-43c (a=19.528); finally at 274K disordering of the Cu+ ions increases the symmetry to F-43m, (a=9.794). The phase transition at 274K coincides well with a strong anomaly in electrical conductivity observed in the Arrhenius plot. Diffusion paths for Cu+ ions are evidenced by means of the atomic displacement factors and split model. Influence of the copper stechiometry on the Tc is also discussed.Comment: conference pape

Ferroelectric Phase Transitions in Films with Depletion Charge

We consider ferroelectric phase transitions in both short-circuited and biased ferroelectric-semiconductor films with a space (depletion) charge which leads to some unusual behavior. It is shown that in the presence of the charge the polarization separates into `switchable' and `non-switchable' parts. The electric field, appearing due to the space charge, does not wash out the phase transition, which remains second order but takes place at somewhat reduced temperature. At the same time, it leads to a suppression of the ferroelectricity in a near-electrode layer. This conclusion is valid for materials with both second and first order phase transitions in pure bulk samples. Influence of the depletion charge on thermodynamic coercive field reduces mainly to the lowering of the phase transition temperature, and its effect is negligible. The depletion charge can, however, facilitate an appearance of the domain structure which would be detrimental for device performance (fatigue). We discuss some issues of conceptual character, which are generally known but were overlooked in previous works. The present results have general implications for small systems with depletion charge.Comment: 11 pages, REVTeX 3.1, five eps-figures included in the text. Minor clarifications in the text. To appear in Phys. Rev. B 61, Apr 1 (2000