Ba2LnFeNb4O15 (Ln = Pr, Nd, Sm,
and Eu) single crystals were grown from high-temperature solution
under controlled atmosphere. Chemical, structural, and dielectric
characterizations were performed on four crystals with tetragonal
tungsten bronze (TTB) structure. The main difference between the four
crystals’ compositions is the proportion of rare-earth, as
well as vacancies, located in the square site. All crystals displayed
an incommensurately modulated structure at room temperature in the
paraelectric state. The corresponding basic structures were refined
using the P4/mbm space group (R = 0.0274; 0.0416; 0.0328; 0.0357 for Ln = Pr, Nd, Sm,
and Eu, respectively). Examination of the structural parameters confirmed
the central role played by square-shaped channels in the crystal chemistry
of these materials. All crystals display a relaxor behavior with T
m (1 MHz) ranging from 110 to 270 K. The chemical,
structural, and physical properties of the crystals are discussed
and compared, for the latter, with those of corresponding ceramics.
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