Conditions Extrêmes et Matériaux : Haute Température et Irradiation

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X.Yang, T.Kyzzhibek, C.Genevois, W.Cao, F.Porcher, X.Kuang*, M.Allix*, 'Ba8CoNb6–xTaxO24 Eight-Layer Shifted Hexagonal Perovskite Ceramics with Spontaneous Ta5+ Ordering and Near-Zero τf', Inorg. Chem. 58 10974-10982 (2019) doi:10.1021/acs.inorgchem.9b01417

Highly positive temperature coefficients of the resonant frequency (τf) of eight-layer hexagonal perovskites are hardly tunable, hindering their application as microwave dielectric resonators. Here, we show that a near-zero τf (∼0.48 ppm °C–1) can be achieved on eight-layer shifted hexagonal perovskite Ba8CoNb4Ta2O24, along with a permittivity εr of ∼30.6 and a Qf of ∼36400 GHz, through substitution of Ta for Nb, satisfying the resonator application requirement. The decrease in the τf of Ba8CoNb6–xTaxO24 takes place mainly through the decrease in the εr or temperature coefficient of permittivity, owing to the less covalent bonding and lower polarizability of Ta5+ compared to those of Nb5+. Synchrotron and neutron powder diffraction data, scanning transmission electron microscopy–high-angle annular dark field imaging, and atomic-scale X-ray energy dispersive spectroscopy elemental mapping reveal that Ta5+ cations in Ba8CoNb4Ta2O24 are naturally distributed in a partially ordered manner, showing a strong site preference on the Nb layers close to the central Co layer over the most out-of-center distorted Nb layers next to empty octahedral layers. This spontaneous Ta ordering in the niobate host is driven by different covalent bonding nature and second-order Jahn–Teller distortion extents of Ta5+ and Nb5+. The results demonstrate an effective way of substituting more ionic Ta5+ for Nb5+, which decreases the τf to near-zero values for eight-layer hexagonal perovskite niobate dielectrics.