Manipulation of polar order in the “empty” tetragonal tungsten bronzes: Ba4-xSrxDy0.671.33Nb10O30, x = 0, 0.25, 0.5, 1, 2, 3
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A series of “empty” tetragonal tungsten bronze (TTB) ferroelectrics, Ba4-xSrxDy0.67□1.33 Nb 10O30 (x = 0, 0.25, 0.5, 1, 2, 3; □ = vacancy), is reported. With increasing x the unit cell contracts in both the ab plane and c-axis; x ≤ 1 compounds are normal ferroelectrics (FE) with decreasing TC as x increases, while x ≥ 2 are relaxor ferroelectrics (RFE) with associated frequency dependent permittivity peaks and with similar Tm and Tf (Vogel-Fulcher freezing temperatures) values. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr2+ principally occupies the A2-site (co-occupied by Ba2+ with the A1-site occupied by Dy3+ and vacancies); for x ≥ 2 significant Sr A1-site occupation leads to the observed RFE characteristics. This FE to RFE crossover is consistent with a previously proposed TTB crystal chemical framework where both a decrease in average A-site size and concurrent increase in A1-site tolerance factor (tA1) favour destabilization of long range polar order and relaxor behaviour. The effect of increasing tA1 as a result of Sr occupancy at the A1 site is dominant in the compounds reported here.
Gardner , J & Morrison , F D 2016 , ' Manipulation of polar order in the “empty” tetragonal tungsten bronzes: Ba 4-x Sr x Dy 0.67 1.33 Nb 10 O 30 , x = 0, 0.25, 0.5, 1, 2, 3 ' Applied Physics Letters , vol 109 , no. 7 , 072901 . DOI: 10.1063/1.4960712
Applied Physics Letters
Copyright 2016 the Authors. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at http://dx.doi.org/10.1063/1.4960712
DescriptionJG would like to thank the EPSRC for provision of a studentship via the doctoral training grant (EP/K503162/1).
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