Phase Transitions in Borohydride Perovskites

Abstract

A series of complex hydrides based on the highly dynamic tetrahydroborate anion BH4-and crystallizing in theABX3type lattice has recently been discovered. They present a rare case of a family of iono-covalent hydrides that has a genuine tunable host lattice, making them an interesting new class of host compounds for not only the design of hydrogen storage materials but also hydride-properties related to heavy metals. Amongst these, preliminary results onREE-based luminescence will be discussed in the neat and doped compounds, the Ln2+excited states surprisingly not being subject to significant quenching by B-H vibrations. Unlike oxide- or halide-perovskites some members of theAB(BH4)3group do not evolve to higher symmetries as a function of temperature. We show by means ofin-situsynchrotron X-ray powder diffraction, vibrational spectroscopy andab initiocalculations in the solid state, that temperature-induced structural distortions in perovskite-typeACa(BH4)3(A= K, Rb, Cs) have their origin in close hydridic di-hydrogen contacts of repulsive nature. Coupling between internal B-H vibrations and phonons results in lattice distortions that are identical in symmetry to well-known instabilities (soft modes) in perovskites, which generally condense to lower temperatures. Anion-substitution BH4-<->X-(X= Halide) calculated on ordered models can relax distortions caused by repulsive effects. High temperature phase-transitions inACa(BH4)3can be of first or second-order, including 2-fold superlattices, simple cubic-cubic transitions accompanied by volume expansion or complex modulated superstructures accompanied by negative volume expansion, as is the case in RbCa(BH4)3. Close di-hydrogen contacts may be suggested as a tool to tailor the crystal symmetry in complex hydride perovskites in the future.