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Effect of iso- and heterovalent cation substitutions on the superionic Faraday transition in fluorite-type modification β-PbF2
Russian version
DOI: 10.21883/PSS.2022.07.54591.328
Sorokin N. I. 1
1Shubnikov Institute of Crystallography “Crystallography and Photonics”, Russian Academy of Sciences, Moscow, Russia
Email: nsorokin1@yandex.ru
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The influence of isovalent substitutions of Pb2+-> Cd2+ and heterovalent substitutions of Pb2+-> Sc3+ on a superionic Faraday transition in Pb1-xCdxF2 (x=0.33) and Pb1-xScxF2+x (x=0.1) solid solutions based on the fluorite-type modification β-PbF2 with sp. gr. Fm 3 m has been studied. The Faraday phase transition can be characterized by the temperature Ttrλ corresponding to maximum on the heat capacity curve and temperature Ttrα corresponding to the beginning of the structural disorder anion sublattice. Both of these temperatures are found on the temperature conductivity dependence sigmadc(T) of β-PbF2, Pb0.67Cd0.33F2 and Pb0.9Sc0.1F2.1 crystals. The values of Ttrλ and Ttrα in solid solutions compared with β-PbF2 (Ttrλ=715±10 K, Ttrα = 597±12 K) decrease by 100-110 and 30-45 K for Pb0.67Cd0.33F2 and Pb0.9Sc0.1F2.1, respectively. Decreasing of temperature Ttrλ leads to an increase in temperature interval of existence of the superionic state. For T>Ttrλ the anionic conductivity of fluorite-type Pb0.67Cd0.33F2, Pb0.9Sc0.1F2.1, and β-PbF2 crystals reaches anomalously high values of sigmadc = 1-2 S/cm (873 K) at an ion transfer activation enthalpy equals to Hsigma~0.3 eV. Keywords: phase transitions, fluorides, fluorite structure, ionic conductivity, solid solutions.
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