Phase diagram and phase transitions in ferroelectric tris-sarcosine calcium chloride and its brominated isomorphs

Abstract

Tris-sarcosine calcium chloride [(TSCC), (CH3NHCH 2COOH)3CaCl2] is a uniaxial ferroelectric (FE) with a displacive second-order phase transition near Tc=130 K. A continuous range of solid solutions can be made by substituting Br for Cl, which lowers Tc to 0 K at ∼72% Br. Such a quantum critical point differs from that in pseudocubic FEs, such as O-18 SrTiO3 or doped KTaO3. For many years, this system was thought to have only two phases, paraelectric and FE, at ambient pressure. However, we find from dielectric and resonant ultrasound spectroscopy that there are four phase transitions in TSCC and in TSCC:Br (for 0 < Br T > 185 K, disordered; Pnma with Z=4(D2h16)185K>T>130K (ordered); Pn21a with Z=4(C2v9)130K>T>64K (FE); P21a (C2h5) with Z =4, 64 K > T > 45 K (not AFE); T < 45 K, unknown structure. A sixth hexagonal structure at high temperatures (>500 K) is hypothesized to be D6h3(P6 3/mcm) with Z =2, but the samples decompose first at 503 K (230 °C). © 2011 American Physical Society.